WO2013125315A1

WO2013125315A1 - Method for concentrating plate-making process effluent, and method for recycling plate-making process effluent

Info

Publication number: WO2013125315A1
Application number: PCT/JP2013/052106
Authority: WO
Inventors: 充弘今泉; 年宏渡辺
Original assignee: 富士フイルム株式会社
Priority date: 2012-02-20
Filing date: 2013-01-30
Publication date: 2013-08-29
Also published as: JPWO2013125315A1; CN104115069A; JP5695267B2; EP2818930A1; CN104115069B; US20140345483A1; EP2818930A4; EP2818930B1

Abstract

A method for concentrating a plate-making process effluent from a photosensitive lithographic printing plate precursor, comprising: simultaneously performing desensitization and development of a photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer on a support, using a developing liquid in which the content of an organic solvent having a boiling point of 100-300°C is 2 mass% or less and which contains 1-10 mass% of a surfactant having a phenyl group or a naphthyl group, and an ethylene oxide group or a propylene oxide group in one development bath of an automatic developing machine; evaporation concentrating a plate-making process effluent generated by the above process to 1/2 to 1/10 volume in an effluent concentrating device; and condensing water vapor separated in the evaporation concentration to generate reclaimed water.

Description

Method for concentrating and recycling platemaking wastewater

The present invention relates to a method for concentrating and recycling a platemaking process waste liquid generated by simultaneously performing a development process and a desensitizing process in a development bath when a photosensitive lithographic printing plate precursor is subjected to a platemaking process using an automatic processor.

Conventionally, when a photosensitive lithographic printing plate precursor is developed with an automatic processor, the concentration and pH of components lost during processing and aging are kept constant, and a developer replenisher is added to maintain the performance of the developer. A means for supplying the developer in the process is employed. Even if such replenishment is performed, if the performance of the developer falls outside the allowable limit, all of the developer is discarded. Since the plate-making process waste liquid has strong alkalinity, it cannot be discharged as general wastewater as it is, and it is necessary for the plate-making company to install waste liquid treatment equipment or to entrust the treatment to a waste liquid treatment company.

However, the method of consigning to a waste liquid treatment company requires a large space for storing the waste liquid and is extremely expensive in terms of cost. In addition, the waste liquid treatment equipment has a problem that the initial investment is extremely large and a considerably large place is required for maintenance.

In order to solve such problems, a technique has been proposed in which the developer is made to have a low pH, and further, a desensitization treatment is simultaneously performed during the development processing to reduce waste liquid discharged (see, for example, JP-A-2008-233660). ).
Also, a method of concentrating the waste liquid by blowing warm air into the waste liquid storage tank (see, for example, JP-A-5-341535) or a method of neutralizing the treatment waste liquid and adding an aggregating agent to agglomerate the aggregating component ( For example, Japanese Patent Laid-Open No. 2-157084) has been proposed.
In addition, a planographic printing plate making waste liquid reduction device that can reduce the discharge amount of the plate making waste liquid and can easily reuse water generated in the process of the plate making waste liquid has been proposed (for example, Japanese Patent No. 4774124). See the publication.)
On the other hand, with respect to the problem of lithographic printing plate development processing waste liquid, it has been proposed to use a developing solution containing a non-reducing sugar and a base from the viewpoint of formulation of a lithographic printing plate developer (for example, JP (See 2011-90282). However, in the current situation, it is not possible to sufficiently solve the problems related to waste liquid treatment only by changing the formulation of the developer.

In the waste liquid concentration technique using hot air, the amount of evaporation is not large, so the effect of reducing the amount of waste liquid is not sufficient, and there is a problem that it takes a long time to sufficiently concentrate the platemaking waste liquid. Furthermore, the treatment of evaporated water has not been studied.
In the technology using the flocculant, there is a problem that the cost of the waste liquid treatment is high. Further, when the plate making waste liquid contains a polymer compound, the solid matter remaining in the evaporation kettle is evaporated in a bowl shape. There is a problem that the maintenance is complicated such that it adheres to the wall surface of the pot and is easily soiled, and the piping of the waste liquid treatment apparatus is easily clogged.

The present invention, which has been made in consideration of the above-mentioned problems, is that foaming at the time of concentration of the waste liquid generated during the plate-making process in which the development process and the desensitization process are simultaneously performed with the developer in the development processing bath of the automatic processor. It is an object of the present invention to provide a method for concentrating a platemaking process waste liquid that is suppressed and efficiently concentrated, and that can be easily cleaned such as a concentration kettle.
Further, the present invention recycles the reclaimed water obtained when concentrating the plate-making process waste liquid, so that there is little contamination due to accumulation of deposits in the developing bath of the automatic processor, and the plate-making process is continuously performed for a long time. It is an object of the present invention to provide a method for recycling a platemaking waste liquid in which the generation of precipitates is suppressed even in the case where it is performed.

As a result of intensive studies to solve the above problems, it has been found that the above problems can be solved by using a developer containing a specific surfactant when simultaneously performing development and desensitization in a developing bath. The present invention has been completed. That is, the configuration of the present invention is as follows.
[1] The photosensitive lithographic printing plate precursor after the exposure in one development processing bath of an automatic developing machine that develops the photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on the support after exposure. In contrast, an organic compound containing 1% by mass to 10% by mass of a surfactant having a phenyl group or naphthyl group and at least one of an ethylene oxide group or a propylene oxide group and having a boiling point in the range of 100 ° C. to 300 ° C. A plate making process step in which the development process and the desensitization process are simultaneously performed with a developer having a solvent content of 2% by mass or less and a boiling point of substantially lower than 100 ° C. or higher than 300 ° C. The platemaking process waste liquid generated by the platemaking process is evaporated and concentrated with a waste liquid concentrator so that the ratio of the volume of the platemaking process liquid after concentration / the volume of the platemaking process waste liquid before concentration is 1/2 to 1/10. A method for concentrating a plate making process waste liquid of a photosensitive lithographic printing plate precursor comprising: a waste liquid concentration step, and a reclaimed water generation step of condensing the water vapor separated in the waste liquid concentration step to generate reclaimed water.
[2] The method for concentrating a platemaking treatment waste liquid of a photosensitive lithographic printing plate precursor as described in [1], wherein the pH of the developer is 6 to 10.

[3] The photosensitive lithographic printing plate precursor after the exposure in one development processing bath of an automatic processor that develops the photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on the support after exposure. In contrast, the surfactant contains 1% by mass to 10% by mass of a surfactant having a phenyl group or a naphthyl group and at least one of an ethylene oxide group and a propylene oxide group, and has a boiling point in the range of 100 ° C. to 300 ° C. A plate making process step in which a development process and a desensitization process are performed simultaneously with a developer having an organic solvent content of 2% by mass or less and having a boiling point lower than 100 ° C. or higher than 300 ° C. The platemaking process waste liquid generated in the platemaking process is evaporated and concentrated by a waste liquid concentrator so that the ratio of the volume of the platemaking process liquid after concentration / the volume of the platemaking process waste liquid before concentration is 1/2 to 1/10. Abandonment A condensing step, a reclaimed water generating step for condensing the water vapor separated in the waste liquid concentrating step to generate reclaimed water, and a reclaimed water supplying step for supplying the reclaimed water obtained in the reclaimed water generating step to the automatic processor. Recycling method for plate making waste liquid of photosensitive lithographic printing plate precursor.

[4] The method for recycling a platemaking treatment waste liquid according to [3], wherein the surfactant has 5 to 30 of at least one of the ethylene oxide group and the propylene oxide group.
[5] The developer further contains at least one compound represented by the following general formula <1>, general formula <2>, and general formula <3>. The method for recycling a platemaking waste liquid according to [3] or [4], wherein the total content of the compounds represented by formula <2> and general formula <3> in the developer is less than 10% by mass.

In the general formula <1>, R ¹ represents a hydrogen atom, an alkyl group, or a substituent having the following structure. A represents a hydrogen atom, an alkyl group, a monovalent substituent including an ethylene oxide group, a monovalent substituent including a carboxylic acid group, or a monovalent substituent including a carboxylate, and B represents an ethylene oxide group. The monovalent substituent containing, the monovalent substituent containing a carboxylic acid group, or the monovalent substituent containing a carboxylate is represented.

In the above formula, R ⁸ represents a hydrogen atom or an alkyl group.
In the general formula <2>, R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and at least one of R ² and R ³ has a substituent. Represents an optionally substituted alkyl group.
D represents an alkyl group or a monovalent substituent containing an ethylene oxide group, and E represents a monovalent substituent containing a carboxylate anion or a monovalent substituent containing an oxide anion (O ⁻ ).
In the general formula <3>, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group, and Z ⁻ represents a counter anion.

[6] The method for recycling a platemaking waste liquid according to any one of [3] to [5], wherein the developer has a pH of 6 to 10.
[7] The method further includes drying the lithographic printing plate obtained by performing the development process and the desensitizing process on the photosensitive lithographic printing plate precursor after the exposure, [3] to [6 ] The recycling method of the platemaking process waste liquid of any one of.
[8] Before performing the development process and the desensitization process, the exposed photosensitive lithographic printing plate precursor is subjected to a heat treatment, and the exposed photosensitive lithographic printing plate precursor is subjected to the development process. The method of recycling a platemaking waste liquid according to any one of [3] to [6], further comprising: drying the lithographic printing plate obtained by performing the desensitization treatment and the desensitization treatment.
[9] The method for recycling a platemaking process waste liquid according to any one of [3] to [8], wherein the waste liquid concentrator has a heating means.
[10] The method for recycling a platemaking waste liquid according to [9], wherein the heating by the heating means included in the waste liquid concentrator is performed in a reduced pressure state.

[11] The heating means included in the waste liquid concentrating device is a heat pump including a heat radiating portion and a heat absorbing portion, the plate making waste liquid is heated by the heat radiating portion of the heat pump, and the water vapor is cooled by the heat absorbing portion of the heat pump. [9] or [10].
[12] Any one of [3] to [11], wherein the waste liquid concentration step includes a concentrate recovery step of pressurizing the concentrate of the platemaking process waste liquid concentrated by evaporation and collecting the concentrate in a recovery tank The method for recycling the platemaking waste liquid according to item 1.

According to the present invention, the waste liquid can be reduced by simultaneously performing the development process and the desensitizing process with the developer in the development processing bath of the automatic processor, but the present invention further concentrates the plate-making process waste liquid. As a result, waste liquid to be discarded can be extremely reduced. Further, foaming at the time of concentration of the platemaking process waste liquid is suppressed, and the concentration device can be easily cleaned. Furthermore, there is no mixing of platemaking waste liquid in reclaimed water, no significant increase in viscosity during concentration, or precipitation of solids, and continuous recycling for a long time by recycling the reclaimed water to the developing bath. Even when the plate making process is performed, the waste liquid discarded as the plate making process waste liquid can be extremely reduced.

It is a conceptual diagram which shows the flow of the apparatus which concerns on the recycling method of the platemaking process waste liquid of this invention. It is a conceptual diagram which shows the flow of the development processing apparatus which has the concentration apparatus of the conventional development processing waste liquid. It is a figure of the automatic image development apparatus which performs a development process and gumming simultaneously with a developing bath.

Hereinafter, the present invention will be described in detail.
[Concentration method of plate making waste liquid of photosensitive lithographic printing plate precursor (hereinafter sometimes referred to as waste solution concentration method)]
The waste liquid concentration method of the present invention comprises a photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on a support, which is exposed to light after being exposed in one development processing bath of an automatic processor that develops the photosensitive lithographic printing plate precursor. 1% by mass to 10% by mass of a surfactant having a phenyl group or naphthyl group and at least one of an ethylene oxide group or a propylene oxide group, and a boiling point of 100 ° C. to 300 ° C. The development treatment and the desensitization treatment are simultaneously carried out with a developer having an organic solvent content of 2% by mass or less and a boiling point lower than 100 ° C. or higher than 300 ° C. The ratio of the plate-making process waste liquid volume after concentration to the plate-making process waste liquid volume before concentration is 1/2 to 1/10 in the plate-making treatment process and the plate-making process waste liquid generated by the plate-making treatment process. Sea urchin, waste concentration step evaporation, and a recycled water generation step, to produce reclaimed water to condense the separated steam in the effluent concentration step.

In the photosensitive lithographic printing plate precursor, an image forming layer on a support is exposed to form a latent image, and thereafter, a non-image portion is removed by development to produce a lithographic printing plate. The photosensitive lithographic printing plate precursor used in the present invention is a negative photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer. The exposed area is polymerized and cured, and is unexposed (non-image area) by development. ) Are removed to form an ink receptive image area. In the method of the present invention, it is one of the features that the non-image area removal and the desensitization treatment of the formed image area are performed in one bath in the developing bath of the automatic processor. Thus, the amount of waste liquid is further reduced as compared with the conventional method.
Hereinafter, the waste liquid concentration method of the present invention will be described in the order of steps. The photosensitive lithographic printing plate precursor used and the exposure step prior to the development step will be described later.

[Plate making process]
In the plate making process, the photosensitive lithographic printing after the exposure is carried out in one developing treatment bath of an automatic developing machine that develops the photosensitive lithographic printing plate precursor having a radical polymerizable image recording layer on the support after exposure. 1% by mass to 10% by mass of a surfactant having a phenyl group or a naphthyl group and at least one of an ethylene oxide group or a propylene oxide group, and a boiling point of 100 ° C. to 300 ° C. The development process and the desensitization process are simultaneously performed with a developer having a content of an organic solvent of 2% by mass or less and having a boiling point lower than 100 ° C or higher than 300 ° C.

[Developer]
The developing solution used for developing the photosensitive lithographic printing plate precursor in the method for concentrating and recycling the platemaking waste liquid of the present invention will be described.
In the present specification, unless otherwise specified, the term “developer” is used to include a development initiating solution (a developing solution in a narrow sense) and a developing replenisher.
The developer and development replenisher to which the present invention is applied are developers for developing a photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer, and are used in one development processing bath of an automatic processor. , A developer used for simultaneously performing development and desensitization.
The developer of the present invention contains 1% by mass to 10% by mass of a surfactant having either a phenyl group or a naphthyl group and at least one of an ethylene oxide group and a propylene oxide group (hereinafter referred to as a specific surfactant as appropriate). %, And the content of the organic solvent having a boiling point in the range of 100 ° C. to 300 ° C. is 2% by mass or less and does not substantially contain an organic solvent having a boiling point lower than 100 ° C. or higher than 300 ° C. It is characterized by. In the developing solution of the present embodiment, the content of the organic solvent having a boiling point in the range of 100 ° C. to 300 ° C. is preferably as small as possible, and it is also a preferred mode when not contained. “Substantially no organic solvent having a boiling point lower than 100 ° C. or higher than 300 ° C.” means that the content of the organic solvent having a boiling point lower than 100 ° C. or higher than 300 ° C. is less than 0.2% by mass. It is. The developer according to the present invention preferably does not contain an organic solvent having a boiling point lower than 100 ° C or higher than 300 ° C.
The developer used for developing the photosensitive lithographic printing plate precursor according to the invention contains a specific surfactant described in detail below. Further, from the viewpoint that the development and desensitization can be satisfactorily performed in one bath, the pH of the developer is preferably 6.0 to 11.0, and more preferably 8.0. It is in the range of 10.0.

(Specific surfactant)
The surfactant used in the developer in the waste liquid concentration method of the present invention is not particularly limited as long as it is a surfactant having either a phenyl group or a naphthyl group in the molecule and at least one of an ethylene oxide group and a propylene oxide group. Absent.
In the present specification, the ethylene oxide group refers to the structure represented by the following formula (a), and the propylene oxide group refers to the structure represented by the following formula (b). Are connected in a straight chain to form a polyethylene oxide skeleton or a polypropylene oxide skeleton.

The surfactant contained in the developer is preferably an anionic surfactant or a nonionic surfactant. By using an anionic surfactant or a nonionic surfactant, the active agent concentration latitude can be kept wide, and both the liquid permeability of the unexposed area and the dispersibility of various compounds in the liquid can be achieved.
[Anionic surfactant]
The most suitable anionic surfactant used in the developer is a compound represented by the following general formula (IA) and general formula (IB).
As a preferred developer, 1.0% by mass of at least one anionic surfactant selected from the group consisting of anionic surfactants represented by the following general formula (IA) and general formula (IB) is used. It is a developer for a photosensitive lithographic printing plate precursor contained in a range of ˜10% by mass.

(In general formula (IA) and general formula (IB), R ³ and R ⁵ each independently represents a linear or branched alkylene group having 1 to 5 carbon atoms, and at least 1 R ⁴ and R ⁶ each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms; p and q each independently represent 0, 1 or Y ¹ and Y ² each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms; n and m each independently represents an integer of 1 to 100. n and m When R represents 2 to 100, a plurality of R ³ and R ⁵ may be the same or different from each other; M ⁺ represents Na ⁺ , K ⁺ , Li ⁺ or NH ₄ ⁺ . )

In a preferred embodiment of the present invention, in the general formulas (IA) and (IB), preferred examples of R ³ and R ⁵ are respectively —CH ₂ —, —CH ₂ CH ₂ —, or —CH ₂ CH (CH ₃ ) — is mentioned, and at least one represents —CH ₂ CH ₂ — or —CH ₂ CH (CH ₃ ) —. R ³ and R ⁵ are more preferably —CH ₂ CH ₂ —. Preferred examples of ^{R 4} and ^R _{_{_{_{^6, CH 3, C 2 H 5}}}} , C 3 H 7, C 4 H 9 and the like. Moreover, it is preferable that p and q are 0 or 1, respectively. Y ¹ and Y ² are each preferably a single bond. N and m are each preferably an integer of 3 to 50, more preferably an integer of 5 to 30.

Specific examples of the compound represented by the general formula (IA) or the general formula (IB) include the following compounds.

[Nonionic surfactant]
Another preferred example of the specific surfactant according to the present invention is a nonionic surfactant represented by the following general formula (II-A) or the following general formula (II-B).

(In General Formula (II-A) and General Formula (II-B), R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 100 carbon atoms, and n and m are each independently N is an integer of 0 to 100, provided that neither n nor m is 0.

Specific examples of the compound represented by the general formula (II-A) include polyoxyethylene phenyl ether, polyoxyethylene methyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, and the like. .
Specific examples of the compound represented by the general formula (II-B) include polyoxyethylene naphthyl ether, polyoxyethylene methyl naphthyl ether, polyoxyethylene octyl naphthyl ether, polyoxyethylene nonyl naphthyl ether, and the like. .

In the compounds represented by the general formulas (II-A) and (II-B), the number of repeating units (n) of the polyoxyethylene group is preferably 3 to 50, more preferably 5 to 30. . The number of repeating units (m) of the polyoxypropylene group is preferably 0 to 10, more preferably 0 to 5. When a plurality of oxyethylene groups and oxypropylene groups are linked to form a chain polyalkyleneoxy group, the bond between the oxyethylene group and the oxypropylene group may be a random bond or a block bond Good. In the general formula (II-A) and the general formula (II-B), when n and m are each 1 or more, that is, when the nonionic surfactant has an oxyethylene group and an oxypropylene group, The total of ethylene oxide groups and propylene oxide groups is preferably 5 to 30.
When the nonionic aromatic ether surfactant represented by the general formula (II-A) or the general formula (II-B) is used, it may be used alone or in combination of two or more in the developer. May be used.
Specific examples of the compound represented by formula (II-A) or formula (II-B) are shown below, but the present invention is not limited thereto.

The said specific surfactant can be used individually by 1 type or in combination of multiple types. When two or more types are combined, an embodiment containing only two or more specific anionic surfactants, an embodiment containing two or more specific nonionic surfactants, one or more specific anionic surfactants and one specific nonionic surfactant, respectively Any of the embodiments may be adopted.
The addition amount of the specific surfactant is required to be in the range of 1% by mass to 10% by mass in the developer, preferably in the range of 2% by mass to 10% by mass, and 3% by mass to 10% by mass. It is more preferable from the viewpoint of effect. By adding 1% by mass or more of the specific surfactant in the developer, the developability and the solubility of the image recording layer component in the developer are improved, and it is formed by adjusting the amount to 10% by mass or less. The printing durability of the lithographic printing plate is improved.
In addition, when 2 or more types of specific surfactant are included, the said addition amount shows total amount.

(Other surfactants)
In addition to the specific surfactant described above, the developer used in the present invention is not limited to other surfactants within the range that does not impair the effects of the present invention (for example, phenyl group or naphthyl having a structure different from that of the specific surfactant). And a surfactant that does not contain either an ethylene oxide group or a propylene oxide group) may be used in combination.
Examples of other surfactants that can be used in combination include betaine surfactants represented by the following general formula <1>, general formula <2>, or general formula <3>.

In the above formula, R ⁸ represents a hydrogen atom or an alkyl group.
In the general formula <2>, R ² and R ³ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and at least one of R ² and R ³ has a substituent. Represents an optionally substituted alkyl group.
D represents an alkyl group or a monovalent substituent containing an ethylene oxide group, and E represents a monovalent substituent containing a carboxylate anion or a monovalent substituent containing an oxide anion (O ⁻ ).
In the general formula <3>, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group, and Z ⁻ represents a counter anion.
The

In the above general formula <1> and general formula <2>, the ethylene oxide group contained in the monovalent substituent containing an ethylene oxide group is — (CH ₂ CH ₂ O) _n H (n is an integer of 1 or more, Preferably, it means 2 to 20), and the monovalent substituent containing an ethylene oxide group mentioned here includes an ethylene oxide group.
In the general formula <1>, the monovalent substituent containing a carboxylic acid group includes the case of only a carboxylic acid group. In the general formula <1>, the carboxylate of a group containing a carboxylate means —COOM, and M represents an alkali metal or an alkaline earth metal, and is preferably an alkali metal. The monovalent substituent containing a carboxylate includes a case of carboxylate alone.
In the general formula <2>, the monovalent substituent containing a carboxylate anion includes the case of only a carboxylate anion. In the general formula <2>, the monovalent substituent containing the oxide anion (O ⁻ ) includes the case of the oxide anion alone.

The compound represented by the above general formula <1>, general formula <2> or general formula <3> (hereinafter also referred to as a specific betaine surfactant) is not particularly limited. And compounds represented by the following general formula (I) to general formula (V).

In addition, examples of the specific betaine surfactant include surfactants represented by the following general formula (VI).

In the general formulas (I) to (VI), R ¹¹ represents a hydrogen atom; an alkyl group; or an alkyl group linked through a bond selected from an ester bond, a carbonyl bond, and an amide bond. The alkyl group linked through the bond preferably has 8 to 20 carbon atoms.
R ¹² , R ¹⁵ , R ¹⁸ , R ²⁴ to R ²⁹ each independently represents a hydrogen atom or an alkyl group.
R ¹³ represents a monovalent substituent containing an alkyl group or an ethylene oxide group.
R ¹⁶ represents a monovalent substituent containing a hydrogen atom, an alkyl group, or an ethylene oxide group.
R ²¹ represents a hydrogen atom, an alkyl group, or a group shown below.

In the above formula, R ^* represents a hydrogen atom or an alkyl group.
R ³⁰ represents an alkyl group or a group containing an ethylene oxide group.
R ¹⁴ , R ¹⁷ , R ¹⁹ , R ²⁰ , R ²² , R ²³ and R ³¹ each independently represent an alkylene group or a single bond.

In the betaine-type surfactant included in the general formula (I), N and a carboxyl group may be directly linked, and in this case, R ¹⁴ represents a single bond. In the surfactant represented by the general formula (I), when the total carbon number increases, the hydrophobic portion increases and it becomes difficult to dissolve in an aqueous developer. In this case, mixing with a water-soluble dissolution aid such as an organic solvent or alcohol that aids dissolution will improve, but if the total carbon number becomes too large, the surfactant will be dissolved within the proper mixing range. It is not possible. Here, the total number of carbon atoms of R ¹¹ to R ¹⁴ is preferably 10 to 40, more preferably 12 to 30.
Here, when R ¹¹ to R ¹³ described above are alkyl groups or R ¹⁴ is an alkylene group, the structure thereof may be linear or branched.

The carbon number of R ¹¹ to R ¹⁴ in these compounds (specific betaine surfactants) is influenced by the material used for the image recording layer, particularly the binder. In the case of a binder having a high degree of hydrophilicity, the carbon number of R ¹¹ to R ¹⁴ tends to be relatively small, and when the binder used has a low degree of hydrophilicity, a carbon number of R ¹¹ to R ¹⁴ is preferably large. .
As typical compounds of the betaine type surfactant represented by the general formula (I), the following compounds may be mentioned.

In addition, in other surfactants shown below, when the total carbon number increases, the hydrophobic portion increases and it becomes difficult to dissolve in an aqueous developer. It is preferable to select the total carbon number of the surfactant in consideration of the mixing range.
In the betaine surfactant represented by the general formula (II), R ¹⁵ in the formula represents a hydrogen atom or an alkyl group, and R ¹⁶ represents a monovalent group including a hydrogen atom, an alkyl group, or an ethylene oxide group. R ¹⁷ represents an alkylene group or a single bond.
Here, the total number of carbon atoms of R ¹⁵ to R ¹⁷ is preferably 10 to 30, and more preferably 12 to 25.
Here, when R ¹⁵ and R ¹⁶ described above are alkyl groups, or R ¹⁷ is an alkylene group, the structure may be linear or branched.
The carbon number of R ¹⁵ to R ¹⁷ in the betaine surfactant represented by the general formula (II) is appropriately selected in relation to other materials used for the image recording layer. For example, when a binder having a high hydrophilicity is used in combination, the carbon number of R ¹⁵ to R ¹⁷ is preferably relatively small. When a binder having a low hydrophilicity is used in combination, the carbon number of R ¹⁵ to R ¹⁷ is used. A larger one is preferred.
Further, in the above compounds, X ⁺ includes divalent metal ions such as calcium ions and magnesium ions, ammonium ions, hydrogen ions and the like in addition to monovalent metal ions such as potassium ions and sodium ions. Among the surfactants represented by the general formula (II), sodium ions and potassium ions are particularly preferable. Examples of typical surfactants represented by the general formula (II) include those shown below.

In the betaine surfactant represented by the general formula (III), R ¹⁸ is a hydrogen atom or an alkyl group, and R ¹⁹ and R ^{20 each} represents an alkylene group or a single bond.
Here, the total number of carbon atoms of R ¹⁸ to R ²⁰ is preferably 10 to 30, and more preferably 12 to 28.
Here, when R ¹⁸ described above is an alkyl group and R ¹⁹ and R ²⁰ are alkylene groups, the structure may be linear or branched.
The carbon number of R ¹⁸ to R ²⁰ in the betaine surfactant represented by the general formula (III) is appropriately selected in relation to other materials used for the image recording layer. For example, when a binder having a high hydrophilicity is used in combination, the carbon number of R ¹⁸ to R ²⁰ is preferably relatively small. When a binder having a low hydrophilicity is used in combination, the carbon number of R ¹⁸ to R ²⁰ is used. A larger one is preferred.
Further, in the above compounds, for X ⁺ and Y ⁺ , in addition to monovalent metal ions such as potassium ion and sodium ion, divalent metal ions such as calcium ion and magnesium ion, ammonium ion and hydrogen ion are used. It is done. Among the compounds (III), sodium ions and potassium ions are particularly preferable. Typical compounds include those shown below.

In the betaine type surfactant represented by the above general formula (IV), N and ethylene oxide may be directly linked, and in this case, R ²² and R ²³ represent a single bond.
Here, the total number of carbon atoms of R ²¹ to R ²³ is preferably 8 to 50, and more preferably 12 to 40.
Here, when R ²¹ described above is an alkyl group and R ²² and R ²³ are an alkylene group, the structure may be linear or branched.
The carbon number of R ²¹ to R ²³ in the surfactant represented by the general formula (IV) is appropriately selected in relation to other materials used for the image recording layer. For example, when a binder having a high hydrophilicity is used in combination, the carbon number of R ²¹ to R ²³ is preferably relatively small. When a binder having a low hydrophilicity is used in combination, the carbon number of R ²¹ to R ²³ is used. A larger one is preferred.
About m and n showing the number of ethylene oxide, if it becomes large, a hydrophilic degree will increase and stability in water will increase. m and n may be the same number or different numbers. The sum of m and n is preferably 3 to 40, more preferably 5 to 20. Typical compounds include those shown below.

In the betaine surfactant represented by the general formula (V), R ²⁴ to R ²⁷ in the formula are a hydrogen atom or an alkyl group.
Here, the total number of carbon atoms of R ²⁴ to R ²⁷ is preferably 10 to 30, and more preferably 12 to 28.
Here, when R ²⁴ to R ²⁷ described above are an alkyl group, the structure may be linear or branched.
The carbon number of R ²⁴ to R ²⁷ in the surfactant represented by the general formula (V) is appropriately selected in relation to other materials used for the image recording layer. For example, when a binder having a high hydrophilicity is used in combination, the carbon number of R ²⁴ to R ²⁷ is preferably relatively small. When a binder having a low hydrophilicity is used in combination, the carbon number of R ²⁴ to R ²⁷ is used. A larger one is preferred.
Z ⁻ represents a counter anion. Although these are not limited, Cl ⁻ , Br ⁻ , I ^{− and the} like are often used. Typical compounds include those shown below.

In the compound corresponding to the above formula (VI), R ²⁸ and R ²⁹ in the formula represent a hydrogen atom or an alkyl group, and R ³⁰ is a monovalent substituent containing an alkyl group or an ethylene oxide group.
Here, the total number of carbon atoms of R ²⁸ to R ³⁰ is preferably 8 to 30, and more preferably 10 to 28.
Here, when R ²⁸ to R ³⁰ described above are alkyl groups, the structure may be linear or branched.
The number of carbons R ²⁸ to R ³⁰ in the surfactant represented by the general formula (VI) is appropriately selected in relation to other materials used for the image recording layer. For example, when a binder having a high hydrophilicity is used in combination, the carbon number of R ²⁸ to R ³⁰ is preferably relatively small. When a binder having a low hydrophilicity is used in combination, the carbon number of R ²⁸ to R ³⁰ is used. A larger one is preferred.
Typical compounds include those shown below.

The specific betaine surfactant, which is the above-mentioned other surfactant, is usually contained in the developer used in the present invention as desired, but is included to improve the dispersibility of the developed image recording layer components. However, the content is preferably less than 10% by mass with respect to the developer. If the content of the specific betaine surfactant is 10% by mass or more, the member in the developing bath is eroded and may cause a failure of the apparatus.

(Organic solvent)
In the present invention, the developer / development replenisher used for developing the photosensitive lithographic printing plate precursor is an organic solvent having a boiling point in the range of 100 ° C. to 300 ° C. for the purpose of improving the solubility of the image recording layer components. Although a solvent may be contained, the content should be in the range of 2% by mass or less, and it is also preferable when the organic solvent is not contained.
If the boiling point of the organic solvent contained in the developer is lower than 100 ° C, it tends to volatilize, and if it exceeds 300 ° C, it becomes difficult to concentrate.

The organic solvent contained in the developer may be any organic solvent as long as the boiling point is in the range of 100 ° C. to 300 ° C., preferably 2-phenylethanol (boiling point: 219 ° C.), 3-phenyl-1-propanol (boiling point: 238 ° C), 2-phenoxyethanol (boiling point: 244 to 255 ° C), benzyl alcohol (boiling point: 205 ° C), cyclohexanol (boiling point: 161 ° C), monoethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 268 ° C), cyclohexanone (boiling point: 155 ° C), ethyl lactate (boiling point: 155 ° C), propylene glycol (boiling point: 187 ° C), ethylene glycol (boiling point: 198 ° C), γ-butyrolactone (Boiling point: 205 ° C.), N-methylpyrrolidone (boiling point: 202 ° C.), N-ethyl pyrrolidone (Boiling point: 218 ° C), glycerin (boiling point: 290 ° C), propylene glycol monomethyl ether (boiling point: 120 ° C), ethylene glycol monomethyl ether (boiling point: 124 ° C), ethylene glycol monomethyl ether acetate (boiling point: 145 ° C), Diethylene glycol dimethyl ether (boiling point: 162 ° C.) and glycerin (boiling point: 299 ° C.), with benzyl alcohol, diethanolamine, monoethanolamine, γ-butyrolactone, N-methylpyrrolidone and N-ethylpyrrolidone being particularly preferred.
Note that alkali amines described later are also treated as organic solvents in the present invention if the boiling point is in the range of 100 ° C to 300 ° C.

[Organic acid or salt thereof]
The developer according to the present invention contains the specific anionic surfactant and / or specific nonionic surfactant and an alkali agent described later, and preferably has a pH of 6 to 10.
The pH of the developer may be adjusted using a pH adjuster. Examples of pH adjusters include citric acid, malic acid, tartaric acid, gluconic acid, benzoic acid, phthalic acid, p-ethylbenzoic acid, pn-propylbenzoic acid, p-isopropylbenzoic acid, pn-butylbenzoic acid. Organic carboxylic acids such as pt-butyl benzoic acid, pt-butyl benzoic acid, p-2-hydroxyethyl benzoic acid, decanoic acid, salicylic acid, 3-hydroxy-2-naphthoic acid, or metal salts thereof, It preferably contains an ammonium salt or the like.
Among these, citric acid has a function as a buffering agent, and is added as trisodium citrate or tripotassium citrate, for example.
Generally, one or more buffering agents are contained in the developer in a range of 0.05 to 5% by mass, more preferably 0.3 to 3% by mass.

[Water-soluble polymer compound]
The developer according to the present invention may contain a water-soluble polymer compound in order to reinforce the function of protecting the plate surface as a gum solution in the desensitization treatment performed together with development in a developing bath. Good.
Examples of the water-soluble polymer compound used in the developer according to the present invention include soybean polysaccharide, modified starch, gum arabic, dextrin, fibrin derivatives (for example, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, etc.) and modified products thereof, pullulan, Examples include polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone, polyacrylamide and acrylamide copolymers, vinyl methyl ether / maleic anhydride copolymers, vinyl acetate / maleic anhydride copolymers, styrene / maleic anhydride copolymers, and the like. . A preferable acid value of the water-soluble polymer compound is 0 to 3.0 meq / g.

As the soybean polysaccharide, conventionally known ones can be used, for example, Soya Five (manufactured by Fuji Oil Co., Ltd.) as a commercial product, and various grades can be used. What can be preferably used is one in which the viscosity of a 10% by mass aqueous solution is in the range of 1 to 100 mPa / sec.

As modified starch, what is shown by the following general formula (VII) is preferable. As the starch represented by the general formula (VII), any starch such as corn, potato, tapioca, rice and wheat can be used. These starches can be modified by a method of decomposing in the range of 5 to 30 glucose residues per molecule with an acid or an enzyme, and further adding oxypropylene in an alkali.

In general formula (VII), the degree of etherification (degree of substitution) is in the range of 0.05 to 1.2 per glucose unit, n represents an integer of 3 to 30, and m represents an integer of 1 to 3.

Particularly preferable among the water-soluble polymer compounds include soybean polysaccharide, modified starch, gum arabic, dextrin, carboxymethylcellulose, polyvinyl alcohol and the like.
Two or more water-soluble polymer compounds can be used in combination. The content of the water-soluble polymer compound in the developer is preferably from 0.1 to 20% by mass, more preferably from 0.5 to 10% by mass.

[Chelating agent]
Further, the developer may contain a chelating agent for the divalent metal. Examples of divalent metals include magnesium and calcium. Examples of the chelating agent include Na ₂ P ₂ O ₇ , Na ₅ P ₃ O ₃ , Na ₃ P ₃ O ₉ , Na ₂ O ₄ P (NaO ₃ P) PO ₃ Na ₂ , and Calgon (sodium polymetaphosphate). Polyethylene salt of, for example, ethylenediaminetetraacetic acid, its potassium salt, its sodium salt; diethylenetriaminepentaacetic acid, its potassium salt, sodium salt; triethylenetetraminehexaacetic acid, its potassium salt, its sodium salt; hydroxyethylethylenediaminetriacetic acid, its Nitrilotriacetic acid, its potassium salt, its sodium salt; 1,2-diaminocyclohexanetetraacetic acid, its potassium salt, its sodium salt; 1,3-diamino-2-propanoltetraacetic acid, its potassium salt , That natoriu 2-phosphonobutanetricarboxylic acid-1,2,4, its potassium salt, its sodium salt; 2-phosphonobutanone tricarboxylic acid-2,3,4, its potassium 1-phosphonoethanetricarboxylic acid-1,2,2, potassium salt, sodium salt; 1-hydroxyethane-1,1-diphosphonic acid, potassium salt, sodium salt; aminotri ( Organic phosphonic acids such as methylenephosphonic acid), potassium salts thereof, sodium salts thereof, etc., for example, S, S-ethylenediamine disuccinic acid (EDDS ₄ H), S, S-ethylenediamine disuccinic acid 3 soda (EDDS ₃ Na) And biodegradable chelating agents such as tetrasodium glutamate diacetate.
The content of the chelating agent in the developer varies depending on the hardness of the hard water used in the developer and the amount of the chelating agent used. It is contained in the range of 01 to 5% by mass, more preferably 0.01 to 0.5% by mass.

[Defoamer]
When an anionic surfactant is contained in the developer, there is a concern that foaming is particularly likely. Therefore, an antifoaming agent may be added to the developer. When an antifoaming agent is added, it is preferably added at 0.00001% by mass or more, more preferably about 0.0001 to 0.5% by mass with respect to the developer.
The developer according to the present invention may contain a fluorine-based antifoaming agent, a silicone-based antifoaming agent, acetylene alcohol, or acetylene glycol as an antifoaming agent.

As a fluorine-type antifoamer, the compound etc. which are represented by a following formula are mentioned.
Of these, fluorine-based antifoaming agents of HLB 1 to 9, particularly fluorine-based antifoaming agents of HLB 1 to 4 are preferably used. The fluorine-based antifoaming agent is added to the developer as it is or in the form of an emulsion mixed with water or other solvent.

(In the above formula, R represents a hydrogen atom or an alkyl group, Rf represents a fluorocarbon group (about 5 to 10 carbon atoms) in which part or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms, X represents Represents CO or SO ₂ , and n represents an integer of 1 to 10.)

As the silicone-based antifoaming agent, a dialkyl polydioxane, preferably a dimethyl polydioxane shown below, as it is or as an O / W type emulsion,

The following alkoxy poly (ethyleneoxy) siloxane, dimethylpolydioxane modified by introducing a part of carboxylic acid group or sulfonic acid group, or mixing these silicone compounds with water together with generally known anionic surfactants An emulsion is used.

Acetylene alcohol is an unsaturated alcohol having an acetylene bond (triple bond) in the molecule. Acetylene glycol is also called alkynediol, and is an unsaturated glycol having an acetylene bond (triple bond) in the molecule.
More specifically, there are those represented by the following general formulas (1) and (2).

(In the general formula (1), R ¹ represents a linear or branched alkyl group having 1 to 5 carbon atoms.)

(In general formula (2), R ² and R ³ each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms, and a + b is a number from 0 to 30.)
In the general formula (2), examples of the linear or branched alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and an isopentyl group.

The following are mentioned as a further specific example of acetylene alcohol and acetylene glycol.
(1) propargyl alcohol (2) propargyl carbinol (3) 3,5-dimethyl-1-hexyn-3-ol (4) 3-methyl-1-butyn-3-ol (5) 3-methyl-1- Pentin-3-ol (6) 1,4-butynediol (7) 2,5-dimethyl-3-hexyne-2,5-diol (8) 3,6-dimethyl-4-octyne-3,6-diol (9) 2,4,7,9-Tetramethyl-5-decyne-4,7-diol (10) Addition of ethylene oxide to 2,4,7,9-tetramethyl-5-decyne-4,7-diol Things (the following structure)

(11) 2,5,8,11-tetramethyl-6-dodecin-5,8-diol

These acetylene alcohols and acetylene glycols can be obtained on the market, and as commercially available products, for example, Air Products and Chemicals Inc. The trade name Surfinol is known. Specific examples of commercially available products include Surfinol 61 as (3), Orphine B as (4), Orphine P as (5), Olphine Y as (7), Surfynol 82 as (8), Examples of (9) include Surfinol 104 and Orphine AK-02, (10) of Surfynol 400 series, and (11) of Surfynol DF-110D.

[Other additives]
Further, an alkali metal salt of an organic acid or an alkali metal salt of an inorganic acid may be added to the developer as a development regulator. For example, sodium carbonate, potassium, ammonium, sodium citrate, potassium, ammonium and the like may be used alone or in combination of two or more.

In addition, an alkaline agent such as tribasic sodium phosphate, potassium, ammonium, sodium borate, potassium, ammonium, sodium hydroxide, potassium, ammonium, lithium, etc. And monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisotopanol Organic alkali agents such as amine, ethyleneimine, ethylenediamine, pyridine, and tetramethylammonium hydroxide are used alone or in combination of two or more. It may be mixed by.

In addition to the above components, the following components can be used in the developer as required. For example, reducing agents, dyes, pigments, water softeners, preservatives and the like can be mentioned.

In the present invention, since the development process and the desensitization process are performed with a developer in one bath in the plate-making process, the pH of the developer used here is 6.0 to 11 from the viewpoint of the effect. Is preferably 0.0, more preferably 8.0 to 10.0.

(water)
The remaining component of the developer is water. The developer (developing stock solution) according to the present invention is advantageous in terms of transportation by keeping it as a concentrated solution having a lower water content than in use and diluting with water at the time of use. In this case, the degree of concentration is appropriate such that each component does not cause separation or precipitation.

In the plate making process, the above-mentioned developer is used in a developing bath of a general automatic processor, so that the developing process and the desensitizing process can be performed well in one bath.

The development treatment is carried out according to a conventional method at a temperature of about 0 ° C. to 60 ° C., preferably about 15 ° C. to 40 ° C., for example, by immersing the image-exposed photosensitive lithographic printing plate precursor in a developer and rubbing with a brush, spraying Can be performed by a method of spraying a developer and rubbing with a brush.

The development processing step in the present invention can be preferably carried out by an automatic development processor equipped with a developer supply means and a rubbing member. An automatic developing processor using a rotating brush roll as the rubbing member is particularly preferable.
Two or more rotating brush rolls are preferable. Further, it is preferable that the automatic developing processor is provided with a means for removing excess developer such as a squeeze roller and a drying means such as a warm air device after the development processing means. Further, the automatic developing processor may be provided with a preheating means for heat-treating the photosensitive lithographic printing plate precursor after image exposure before the development processing means.
Such processing in an automatic processor has the advantage that it is free from dealing with development residue derived from the protective layer / image recording layer that occurs in the case of so-called on-press development processing.

[Waste liquid concentration process]
In this step, the plate-making process waste liquid generated in the plate-making process step is processed by a waste liquid concentrator so that the ratio of the volume of the plate-making process liquid after concentration to the volume of the plate-making process waste liquid before concentration is 1/2 to 1/10. Concentrate by evaporation.
Hereinafter, the waste liquid concentration process according to the present invention will be described.
In the waste liquid concentrator, the waste liquid is heated without being decompressed or heated under reduced pressure to separate the evaporated water and the remaining concentrate (slurry) into an evaporation pot (not shown), and an organic solvent in the evaporation pot At least a cooling kettle (not shown) that cools and condenses the water separated as water vapor that may contain water to regenerate water.

Concentration of the waste liquid is performed by a method of reducing the boiling point of the waste liquid and concentrating the waste liquid at a lower temperature than under atmospheric pressure by reducing the boiling point of the evaporation pot with a decompression means and heating and concentrating. preferable. By using the decompression means, there is an advantage that the evaporating pot, the waste liquid and the waste liquid concentrate are safer and less susceptible to heat.
Depressurization means include general water-sealed, oil-rotating, and diaphragm-type mechanical vacuum pumps, diffusion pumps using oil and mercury, multistage turbo compressors, reciprocating compressors, screw compressors, and other compressors Among these, an aspirator is preferably used in terms of maintainability and cost.
Examples of the depressurization condition include depressurization until 666.6 Pa (5 mmHg) to 13332.2 Pa (100 mmHg), preferably 666.6 Pa (5 mmHg) to 3999.7 Pa (30 mmHg).
As the heating condition, a temperature range corresponding to 666.6 Pa to 13332.2 Pa, which is a pressure easily obtained with a water pump or a vacuum pump, is selected. Specifically, it is in the range of 20 ° C to 80 ° C, more preferably in the range of 25 ° C to 45 ° C.
Distilling at a high temperature and concentrating requires a large amount of electric power. Therefore, by reducing the pressure, the heating temperature can be lowered and the electric power used can be suppressed.

In addition, it is also preferable to use a heat pump as a heating means in the evaporating pot, and it is preferable that the heat pump includes a heat radiating part and a heat absorbing part. While the platen processing waste liquid is heated by the heat pump heat dissipation part, the water vapor separated from the plate making process waste liquid can be cooled by the heat pump heat absorption part, the waste liquid is heated and concentrated by the heat pump heat generation, and the water vapor condensation is performed by the heat pump. Compared with the case of using a heating means such as an electric heater, the heat absorption is advantageous because the heat absorption is performed, and there are advantages such as no high heat locally, higher safety, and a reduced carbon dioxide emission amount.

In this step, when the platemaking process waste liquid is evaporated and concentrated in the waste liquid concentrating device, the platemaking process waste liquid is heated by a heating means in an evaporation kettle to be ½ to 1/10 (volume basis). = Evaporation concentration so as to be: platemaking process waste liquid after concentration / platemaking process waste liquid before concentration). Here, if the concentration ratio is less than 1/2, the amount of waste liquid to be treated is not effectively reduced, and if the concentration exceeds 1/10, it is concentrated in the evaporation pot of the waste liquid concentrator 30. There is a concern that precipitation of solid matter due to the waste liquid tends to occur, and the maintainability deteriorates. It is preferable to concentrate in the range of 1/3 to 1/8 on a volume basis. When the concentration is within the above range, there is little dirt in the concentration kettle, and continuous operation is possible over a long period of time. Moreover, the obtained reclaimed water can be reused, and there is very little waste liquid to be discarded as the platemaking process waste liquid.
As waste liquid concentrators used in this embodiment, Takagi Chiller heat pump type concentrators XR-2000 and XR-5000 (both are trade names), heating type Cosmotech's friendly series (trade names), etc. Commercial products may be used.

[Reclaimed water generation process]
In this step, the water vapor separated in the waste liquid concentration step is condensed to generate reclaimed water.
As described above, in the waste liquid concentration step, when the heat concentration of the waste liquid is performed by the heat pump, the water vapor cooled by the heat absorbing portion of the heat pump becomes liquid and reclaimed water is obtained. That is, reclaimed water is generated in the waste liquid concentration step.
Further, when the waste liquid is heated and concentrated using a known heating means such as an electric heater, the water vapor is condensed using a cooling means to generate regenerated water. As the cooling means, a known water-cooled cooler or the like may be used as appropriate.

The reclaimed water obtained as described above is reclaimed water having a low BOD and COD value. When the developer used in the present invention is used, the BOD value is approximately 250 mg / L or less and the COD value is 200 mg / L or less. Therefore, excess reclaimed water may be discharged as it is into general waste water. However, when the reclaimed water contains an organic solvent or the like, a treatment with activated sludge or the like is performed before discharge.
Further, as in the recycling method of the present invention to be described later, it is also preferable to recycle recycled water by supplying it to a developing bath as dilution water.

<Recycling method of plate making waste liquid for photosensitive lithographic printing plate precursor>
In the recycling method of the present invention, the photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on a support is exposed and then exposed to light in a single development processing bath of an automatic processor that develops the photosensitive lithographic printing plate precursor. 1% by mass to 10% by mass of a surfactant having a phenyl group or a naphthyl group and at least one of an ethylene oxide group and a propylene oxide group and a boiling point of 100 ° C. to 300 ° C. with respect to the lithographic printing plate precursor The development treatment and the desensitization treatment are simultaneously carried out with a developer having an organic solvent content of 2% by mass or less and a boiling point lower than 100 ° C. or higher than 300 ° C. The ratio of the plate-making process waste liquid volume after concentration to the plate-making process waste liquid volume before concentration is 1/2 to 1/10 in the plate-making treatment process and the plate-making process waste liquid generated by the plate-making treatment process. In addition, a waste liquid concentration step for evaporating and concentrating, a regenerated water generating step for condensing the water vapor separated in the waste liquid concentrating step to generate reclaimed water, and a reclaimed water obtained in the reclaimed water generating step are supplied to the automatic processor. A reclaimed water supply step.
That is, the recycling method of the present invention further includes a reclaimed water supply process in addition to the plate making process, the waste liquid concentrating process, and the reclaimed water generating process in the plate making process waste liquid concentration method of the present invention.
In the recycling method of the present invention, the generated reclaimed water is supplied to a replenishing water tank or the like and used as a diluting water for diluting the developing replenisher at a predetermined magnification in a developing bath disposed in an automatic processor. The developer replenisher may be mixed and used to dilute the developer replenisher to a predetermined magnification.
Further, the reclaimed water generated from the platemaking processing waste liquid generated from a plurality of automatic processors may be collected and used in one replenishing water tank, and further diluted water from the replenishing water tank to a plurality of automatic processors. Or you may supply as rinse water.

Specific examples of the apparatus that can be suitably used in the waste liquid concentration method and the recycling method of the present invention include, for example, a planographic printing plate making process waste liquid reduction apparatus described in Japanese Patent No. 4774124, and Japanese Patent Application Laid-Open No. 2011-90282. The waste liquid processing apparatus described in the gazette etc. is mentioned.
Hereinafter, an exemplary embodiment according to the present invention will be described with reference to the drawings.
As shown in FIG. 1, in the recycling method of the platemaking process waste liquid according to this embodiment, the waste liquid of the developer discharged from the automatic processor 10 and the plate making process of the photosensitive lithographic printing plate precursor is removed. The intermediate tank 20 to be stored and the waste liquid sent from the intermediate tank 20 are heated without heating under reduced pressure or heated under reduced pressure to separate into evaporated water and residual concentrate (slurry) and separated. A waste liquid concentrator 30 is used that cools and condenses water vapor to generate reclaimed water. The reclaimed water is introduced into the reclaimed water tank 50. Further, the waste liquid concentrated by the waste liquid concentrating device 30 is collected in the waste liquid collection tank 40. It is also preferable to transfer the concentrated waste liquid to the waste liquid tank 40 by pressurizing with a pump.

The waste liquid concentrating device 30 is an evaporator (not shown) that separates the waste liquid sent from the intermediate tank 20 into water to be evaporated and residual concentrate (slurry) by heating without heating or under reduced pressure. And a cooling kettle (not shown) that cools and condenses the water separated as water vapor (which may contain an organic solvent) in the evaporation kettle to regenerate water.

A reclaimed water tank 50 for temporarily storing the separated reclaimed water, and a distilled reclaimed water reuse device 60 for controlling the supply of the reclaimed water to the automatic processor 10 are provided. The distilled reclaimed water recycling apparatus 60 preferably includes a replenishing water tank 80 for supplying reclaimed water to the automatic processor 10, piping, a pressure gauge for measuring the pressure in the piping, and a pump. In addition, an analysis device may be provided to analyze the components of the reclaimed water and perform a neutralization, supply of fresh water, and the like according to the components to prepare a composition.
The recovered reclaimed water is supplied from the replenishing water tank 80 to the automatic developing device 10 by controlling the driving of the pump according to the pressure value measured by the pressure gauge provided in the distilled reclaimed water recycling device 60. The A developing replenisher is supplied from the developer replenisher tank 70 to the automatic developing machine 10.

The reclaimed water obtained by this system may contain an organic solvent as long as it is 0.5% or less based on the volume.
The obtained reclaimed water is reclaimed water having a low BOD and COD value. When the developer used in the present invention is used, the BOD value is approximately 250 mg / L or less and the COD value is 200 mg / L or less. Therefore, dilution water for evaporation correction in an automatic processor, dilution water for development replenisher, In addition to rinsing water for washing the plate or washing water for an automatic processor, excess reclaimed water may be discharged as it is into general waste water.

In the present invention, the developing replenisher is diluted and supplied to the developing bath of the automatic processor 10. In FIG. 1, the amount of reclaimed water supplied from the replenishing water tank 80 is controlled in accordance with the amount supplied from the developing replenisher tank 70, and development is performed at a predetermined magnification in a developing tank (not shown) arranged in the automatic developing machine 10. Although an embodiment of diluting the replenisher is shown, the present invention is not limited to this embodiment, and the developer replenisher and regenerated water are mixed in advance, and the developer replenisher is diluted to a predetermined magnification and then supplied into the developing bath. May be.
Further, the platemaking process waste liquid generated from a plurality of automatic processors may be collected in one waste liquid concentrator, and the obtained reclaimed water may be supplied to the plurality of automatic processors as dilution water or rinse water.
By using the reclaimed water as supplementary water in this way, there is also an advantage that the processing amount of the photosensitive lithographic printing plate precursor that is appropriately subjected to plate making processing is increased without newly supplying dilution water or the like. .

[Photosensitive planographic printing plate precursor]
Hereinafter, the photosensitive lithographic printing plate precursor that can be preferably applied in the method for recycling a platemaking waste liquid of the present invention will be described in detail.
The photosensitive lithographic printing plate precursor according to the invention is used without particular limitation as long as it has a radically polymerizable image recording layer on a hydrophilic support.
The radically polymerizable image recording layer usually contains (A) a polymerization initiator, (B) a polymerizable compound, and (C) a sensitizing dye, and further contains (D) a binder polymer as required. It is preferable to have a radical polymerizable image recording layer and a protective layer in this order on the support.
Hereinafter, the components contained in the image recording layer of the photosensitive lithographic printing plate precursor according to the invention will be sequentially described.

(A) Polymerization initiator The image recording layer contains a polymerization initiator (hereinafter also referred to as an initiator compound). In the present invention, a radical polymerization initiator is preferably used.

As the initiator compound, those known to those skilled in the art can be used without limitation, and specifically include, for example, trihalomethyl compounds, carbonyl compounds, organic peroxides, azo compounds, azide compounds, metallocene compounds, hexaarylbiphenyls. Examples include imidazole compounds, organic boron compounds, disulfone compounds, oxime ester compounds, onium salt compounds, and iron arene complexes. Among these, at least one selected from the group consisting of a hexaarylbiimidazole compound, an onium salt compound, a trihalomethyl compound, and a metallocene compound is preferable, and a hexaarylbiimidazole compound is particularly preferable. Two or more polymerization initiators may be used in combination as appropriate.

Examples of the hexaarylbiimidazole compound include lophine dimers described in European Patent 24,629, European Patent 10,7792, US Pat. No. 4,410,621, such as 2,2′-bis (o-chlorophenyl) -4. , 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o , P-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (m-methoxyphenyl) Biimidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o- Trifluoromethylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and the like.
The hexaarylbiimidazole compound is particularly preferably used in combination with a sensitizing dye having a maximum absorption at 300 to 450 nm.

As the onium salt compound, a sulfonium salt, an iodonium salt, or a diazonium salt is preferably used. In particular, diaryliodonium salts and triarylsulfonium salts are preferably used.
The onium salt compound is particularly preferably used in combination with an infrared absorber having a maximum absorption at 750 to 1400 nm.

As other polymerization initiators, polymerization initiators described in paragraph numbers [0071] to [0129] of JP-A-2007-206217 can be preferably used.

The polymerization initiator is preferably used alone or in combination of two or more.
The amount of the polymerization initiator used in the image recording layer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and further preferably 1.0% by mass to the total solid content of the image recording layer. 10% by mass.
In the present specification, “total solid content” means the total amount of components excluding the solvent among all components constituting the image recording layer.

(B) Polymerizable Compound The polymerizable compound used in the image recording layer is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof, and usually polymerizable monomers are used.
Examples of monomers include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters and amides thereof, preferably unsaturated carboxylic acids. Esters of an acid and a polyhydric alcohol compound and amides of an unsaturated carboxylic acid and a polyamine compound are used. Further, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group and the like with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group and an addition reaction product of a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group, A substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, a compound group in which the unsaturated carboxylic acid is replaced with unsaturated phosphonic acid, styrene, vinyl ether or the like can be used. These are disclosed in JP-T-2006-508380, JP-A-2002-287344, JP-A-2008-256850, JP-A-2001-342222, JP-A-9-179296, JP-A-9-179297. JP-A-9-179298, JP-A-2004-294935, JP-A-2006-243493, JP-A-2002-275129, JP-A-2003-64130, JP-A-2003-280187, This is described in, for example, Japanese Laid-Open Patent Publication No. 10-333321.

Specific examples of monomers of esters of polyhydric alcohol compounds and unsaturated carboxylic acids include acrylic acid esters such as ethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, Examples include trimethylolpropane triacrylate, hexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol tetraacrylate, sorbitol triacrylate, isocyanuric acid ethylene oxide (EO) -modified triacrylate, and polyester acrylate oligomer. Methacrylic acid esters include tetramethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, pentaerythritol trimethacrylate, bis [p- (3-methacryloxy-2-hydroxypropoxy) phenyl ] Dimethylmethane, bis- [p- (methacryloxyethoxy) phenyl] dimethylmethane, and the like. Specific examples of amide monomers of polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis-methacrylate. Examples include amide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, and xylylene bismethacrylamide.
Further, various compounds may be appropriately selected and used as described in paragraph numbers [0189] to [0208] of JP-A-2004-318053.

Further, urethane-based addition-polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinylurethane compound containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups Etc.

_{^{_{CH 2 = C (R 4)}}} COOCH 2 CH (R 5) OH (A)
(However, R ⁴ and R ⁵ represent H or CH _3. )

Also, urethanes as described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-A-2003-344997, JP-A-2006-65210 are disclosed. Acrylates, JP-B 58-49860, JP-B 56-17654, JP-B 62-39417, JP-B 62-39418, JP-A 2000-250211, JP-A 2007-94138 Urethane compounds having an ethylene oxide skeleton described in the publication, US Pat. No. 7,153,632, JP-T 8-505958, JP-A 2007-293221, and JP-A 2007-293223. Urethane compounds having a hydrophilic group are also suitable.

Also, photo-oxidizable polymerizable compounds described in JP-T-2007-506125 are suitable, and polymerizable compounds containing at least one urea group and / or tertiary amino group are particularly preferred. Specific examples include the following compounds.

Details of the method of use such as the structure of the polymerizable compound, whether it is used alone or in combination, and the amount added can be arbitrarily set according to the performance design of the final photosensitive lithographic printing plate precursor.
The polymerizable compound is preferably used in the range of 5 to 75% by mass, more preferably 25 to 70% by mass, and particularly preferably 30 to 60% by mass with respect to the total solid content of the image recording layer.

(C) Sensitizing dye The image recording layer contains a sensitizing dye. The sensitizing dye is not particularly limited as long as it absorbs light at the time of image exposure to be in an excited state, supplies energy to the polymerization initiator by electron transfer, energy transfer or heat generation, and improves the polymerization start function. Can be used. In particular, a sensitizing dye having a maximum absorption at 300 to 450 nm or 750 to 1400 nm is preferably used.

Examples of the sensitizing dye having maximum absorption in the wavelength range of 300 to 450 nm include merocyanines, benzopyrans, coumarins, aromatic ketones, anthracenes, styryls, oxazoles and the like.

Among the sensitizing dyes having an absorption maximum in the wavelength range of 300 nm to 450 nm, more preferable dyes from the viewpoint of high sensitivity include dyes represented by the following general formula (IX).

In General Formula (IX), A represents an aryl group or a heteroaryl group which may have a substituent, and X represents an oxygen atom, a sulfur atom, or ═N (R ³ ). R ¹ , R ² and R ³ each independently represent a monovalent nonmetallic atomic group, and A and R ¹ or R ² and R ³ are bonded to each other to form an aliphatic or aromatic ring May be formed.

General formula (IX) will be described in more detail. R ¹ , R ² and R ³ are each independently
Monovalent non-metal atomic group, preferably hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, substituted Alternatively, it represents an unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

As the aryl group or heteroaryl group which may have a substituent represented by A in general formula (IX), a substituted or unsubstituted aryl group, a substituted or an unsubstituted group described by R ¹ , R ² and R ³ , respectively. The thing similar to an unsubstituted heteroaryl group is mentioned.

Specific examples of such a sensitizing dye include paragraph numbers [0047] to [0053] of JP-A-2007-58170, paragraph numbers [0036] to [0037] of JP-A-2007-93866, and JP-A-2007-72816. The compounds described in paragraph Nos. [0042] to [0047] are preferably used.

Also, JP 2006-189604, JP 2007-171406, JP 2007-206216, JP 2007-206217, JP 2007-225701, JP 2007-225702, and JP 2007-316582. Sensitizing dyes described in JP-A-2007-328243 can also be preferably used.

Next, a sensitizing dye having a maximum absorption at 750 to 1400 nm (hereinafter sometimes referred to as “infrared absorber”) will be described. As the infrared absorber, a dye or a pigment is preferably used.

As the dye, commercially available dyes and known dyes described in documents such as “Dye Handbook” (edited by the Society for Synthetic Organic Chemistry, published in 1970) can be used. Specifically, dyes such as azo dyes, metal complex azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes Is mentioned.
Particularly preferred among these dyes are cyanine dyes, squarylium dyes, pyrylium salts, nickel thiolate complexes, and indolenine cyanine dyes. Further, cyanine dyes and indolenine cyanine dyes are preferred, and particularly preferred examples include cyanine dyes represented by the following general formula (a).

In the general formula (a), X ¹ represents a hydrogen atom, a halogen atom, —NPh ₂ , —X ² -L ¹ or a group shown below. Here, X ² represents an oxygen atom, a nitrogen atom or a sulfur atom, L ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, an aryl group having a hetero atom (N, S, O, halogen atom, Se) And represents a hydrocarbon group having 1 to 12 carbon atoms including a hetero atom. X _a ^- is _{Z a} to be described later ^- is synonymous with, ^{R a} represents a hydrogen atom, an alkyl group, an aryl group, a substituted or unsubstituted amino group,
Represents a substituent selected from a halogen atom.

R ¹ and R ² each independently represents a hydrocarbon group having 1 to 12 carbon atoms. In view of storage stability of the image recording layer coating solution, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms. R ¹ and R ² may be connected to each other to form a ring, and when a ring is formed, it is particularly preferable to form a 5-membered ring or a 6-membered ring.

Ar ¹ and Ar ² may be the same or different and each represents an aryl group which may have a substituent. Preferred aryl groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a C12 or less hydrocarbon group, a halogen atom, and a C12 or less alkoxy group are mentioned. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ⁴ may be the same or different and each represents a hydrocarbon group having 20 or less carbon atoms which may have a substituent. Preferred substituents include alkoxy groups having 12 or less carbon atoms, carboxyl groups, and sulfo groups. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, a hydrogen atom is preferred. Z _a ^- represents a counter anion.
However, when the cyanine dye represented by the general formula (a) has an anionic substituent in its structure and neutralization of charge is not necessary, Z _a ^- is not necessary. Preferred Z _a ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, and a sulfonate ion, particularly preferably a perchlorate ion, from the storage stability of the image recording layer coating solution. , Hexafluorophosphate ions, and aryl sulfonate ions.

Specific examples of the cyanine dye represented by the general formula (a) that can be suitably used include paragraph numbers [0017] to [0019] of JP-A No. 2001-133969, paragraph numbers of JP-A No. 2002-023360 [0016] ] To [0021], compounds described in paragraph numbers [0012] to [0037] of JP-A No. 2002-040638, preferably paragraph numbers [0034] to [0041] of JP-A No. 2002-278057, JP-A 2008- The compounds described in paragraph Nos. [0080] to [0086] of No. 195018, particularly preferably the compounds described in paragraph Nos. [0035] to [0043] of JP-A-2007-90850 are exemplified.

Further, compounds described in paragraph numbers [0008] to [0009] of JP-A No. 5-5005 and paragraph numbers [0022] to [0025] of JP-A No. 2001-222101 can also be preferably used.

Only one type of infrared absorbing dye may be used, or two or more types of infrared absorbing dyes may be used in combination. Infrared absorbing agents other than infrared absorbing dyes such as pigments may be used in combination. As the pigment, compounds described in paragraph numbers [0072] to [0076] of JP-A-2008-195018 are preferable.

A preferred addition amount of the sensitizing dye is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and particularly preferably 0.2 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. 10 parts by mass.

(D) Binder polymer The image recording layer may contain a binder polymer.
As the binder polymer, a polymer that can carry the image recording layer component on the support and can be removed by a developer is used. As the binder polymer, (meth) acrylic polymer, polyurethane resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyvinyl formal resin, polyamide resin, polyester resin, epoxy resin and the like are used. In particular, (meth) acrylic polymers, polyurethane resins, and polyvinyl butyral resins are preferably used.

In the present invention, “(meth) acrylic polymer” means (meth) acrylic acid, (meth) acrylic acid ester (alkyl ester, aryl ester, allyl ester, etc.), (meth) acrylamide, and (meth). A copolymer having a (meth) acrylic acid derivative such as an acrylamide derivative as a polymerization component. “Polyurethane resin” refers to a polymer produced by a condensation reaction of a compound having two or more isocyanate groups and a compound having two or more hydroxyl groups. “Polyvinyl butyral resin” refers to a polymer synthesized by reacting polyvinyl alcohol obtained by saponifying part or all of polyvinyl acetate and butyraldehyde under an acidic condition (acetalization reaction). The polymer which introduce | transduced the acid group etc. by the method etc. by making the compound which has the hydroxyl group and acid group etc. which were made react is also contained.

A preferred example of the (meth) acrylic polymer in the present invention includes a copolymer having a repeating unit containing an acid group. Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphonic acid group, a phosphoric acid group, and a sulfonamide group, and a carboxylic acid group is particularly preferable. As the repeating unit containing an acid group, a repeating unit derived from (meth) acrylic acid or one represented by the following general formula (i) is preferably used.

In general formula (i), R ¹ represents a hydrogen atom or a methyl group, and R ² represents a single bond or an n + 1 valent linking group. A represents an oxygen atom or —NR ³ —, and R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. n represents an integer of 1 to 5.

The linking group represented by R ² in the general formula (i) is composed of a hydrogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom, and the number of atoms is preferably 1 to 80 is there.
The proportion (mol%) of the copolymer component having a carboxylic acid group in the total copolymer components of the (meth) acrylic polymer is preferably 1 to 70% from the viewpoint of developability. Considering compatibility between developability and printing durability, it is more preferably 1 to 50%, and particularly preferably 1 to 30%.
Such a binder polymer is described in paragraph numbers [0018] to [0127] of JP-A No. 2004-318053, and the compounds described herein are preferably used as the binder polymer in the present invention.

The (meth) acrylic polymer used as the binder polymer may further have a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that crosslinks the polymer in the course of radical polymerization reaction that occurs in the image recording layer when the photosensitive lithographic printing plate precursor is exposed. For example, it can undergo an addition polymerization reaction. Examples of the functional group include an ethylenically unsaturated bond group, an amino group, and an epoxy group. Moreover, the functional group which can become a radical by light irradiation may be sufficient, and as such a crosslinkable group, a thiol group, a halogen group, etc. are mentioned, for example. Of these, an ethylenically unsaturated bond group is preferable. As the ethylenically unsaturated bond group, a styryl group, a (meth) acryloyl group, and an allyl group are preferable.

The content of the crosslinkable group in the (meth) acrylic polymer (content of unsaturated double bond capable of radical polymerization by iodine titration) is preferably 0.01 to 10.0 mmol per gram of the polymer. The amount is preferably 0.05 to 9.0 mmol, particularly preferably 0.1 to 8.0 mmol.

As a suitable example of the polyurethane resin used as the binder polymer in the present invention, paragraph numbers [00099] to [0210] of JP-A No. 2007-187836, paragraph numbers [0019] to [0100] of JP-A No. 2008-276155 are mentioned. Examples thereof include polyurethane resins described in paragraph numbers [0018] to [0107] of JP-A-2005-250438 and paragraph numbers [0021] to [0083] of JP-A-2005-250158.
Preferable examples of the polyvinyl butyral resin used as the binder polymer in the present invention include polyvinyl butyral resins described in paragraph numbers [0006] to [0013] of JP-A No. 2001-75279.

A part of the acid groups in the binder polymer may be neutralized with a basic compound. Examples of basic compounds include compounds containing basic nitrogen, alkali metal hydroxides, and quaternary ammonium salts of alkali metals.
The binder polymer preferably has a mass average molecular weight of 5,000 or more, more preferably 10,000 to 300,000, and a number average molecular weight of 1,000 or more, preferably 2,000 to 250,000. More preferred. The polydispersity (mass average molecular weight / number average molecular weight) is preferably 1.1 to 10.
A binder polymer may be used independently or may be used in mixture of 2 or more types.
The content when the binder polymer is used in the image recording layer is preferably 5 to 75% by mass with respect to the total solid content of the image recording layer, from the viewpoint of good strength of the image area and image formability. 70% by mass is more preferable, and 10 to 60% by mass is even more preferable.
The total content of the polymerizable compound and the binder polymer is preferably 90% by mass or less with respect to the total solid content of the image recording layer. If it exceeds 90% by mass, the sensitivity and developability may be lowered. More preferably, it is 35 to 80% by mass.

(Chain transfer agent)
The image recording layer preferably contains a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by Polymer Society, 2005), pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate a radical by donating hydrogen to a radical species having low activity, or can be oxidized and then deprotonated to generate a radical. In the image recording layer according to the present invention, in particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) ) Can be preferably used.

The addition amount of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1 to 5 parts by mass with respect to 100 parts by mass of the total solid content of the image recording layer. .

(Other image recording layer components)
The image recording layer can further contain various additives as required. Additives include surfactants for improving developability and improving the surface of the coating, microcapsules for achieving both developability and printing durability, and improving the developability and dispersion stability of microcapsules. Hydrophilic polymer, colorant and print-out agent for visually recognizing image area and non-image area, polymerization inhibitor for preventing unnecessary thermal polymerization of radical polymerizable compound during production or storage of image recording layer Hydrophobic low molecular weight compounds such as higher fat derivatives to prevent polymerization inhibition by oxygen, inorganic fine particles and organic fine particles for improving the cured film strength of the image area, hydrophilic low molecular weight compounds for improving developability, sensitivity Examples thereof include a co-sensitizer for improvement and a plasticizer for improvement of plasticity. These additives are all known, for example, paragraph numbers [0161] to [0215] of JP-A-2007-206217, paragraph number [0067] of JP-T-2005-509192, and JP-A-2004-310000. The compounds described in paragraphs [0023] to [0026] and [0059] to [0066] can be used. As for the surfactant, a surfactant which may be added to the developer described later can also be used.

<Formation of image recording layer>
The image recording layer is formed by preparing or applying a coating solution by dispersing or dissolving the necessary components described above in a solvent. Examples of the solvent to be used include methyl ethyl ketone, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, γ-butyrolactone, and the like. Is not to be done. A solvent is used individually or in mixture. The solid content concentration of the coating solution is preferably 1 to 50% by mass.

The coating amount (solid content) of the image recording layer obtained after coating and drying is preferably from 0.3 to 3.0 g / m ² . Various methods can be used for application. Examples thereof include bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating, and roll coating.

<Protective layer>
In the photosensitive lithographic printing plate precursor according to the present invention, a protective layer (oxygen blocking layer) is provided on the image recording layer in order to block diffusion and penetration of oxygen that hinders the polymerization reaction during exposure. As a material for the protective layer, either a water-soluble polymer or a water-insoluble polymer can be appropriately selected and used, and two or more kinds can be mixed and used as necessary. Specific examples include polyvinyl alcohol, modified polyvinyl alcohol, polyvinyl pyrrolidone, water-soluble cellulose derivatives, poly (meth) acrylonitrile, and the like. Among these, it is preferable to use a water-soluble polymer having relatively excellent crystallinity, and specifically, polyvinyl alcohol as the main component is most excellent in basic characteristics such as oxygen barrier properties and development removability. Give a good result.
The polyvinyl alcohol used for the protective layer may be partially substituted with an ester, an ether or an acetal as long as it contains an unsubstituted vinyl alcohol unit for having necessary oxygen barrier properties and water solubility. Similarly, some of them may have other copolymer components. Polyvinyl alcohol can be obtained by hydrolyzing polyvinyl acetate. Specific examples of polyvinyl alcohol include those having a hydrolysis degree of 69.0 to 100 mol% and a number of polymerization repeating units of 300 to 2400. Can do. Specific examples include compounds described in paragraph numbers [0233] to [0234] of JP-A No. 2004-318053.
The content of polyvinyl alcohol in the protective layer is preferably 20 to 95% by mass, more preferably 30 to 90% by mass.

Also, known modified polyvinyl alcohol can be preferably used. In particular, acid-modified polyvinyl alcohol having a carboxylic acid group or a sulfonic acid group is preferably used. Specific examples include polyvinyl alcohols described in JP-A-2005-250216 and JP-A-2006-259137.

In the case of using a mixture of polyvinyl alcohol and another material, as a component to be mixed, modified polyvinyl alcohol, polyvinyl pyrrolidone or a modified product thereof is preferable from the viewpoint of oxygen barrier properties, development removability, and the content in the protective layer is It is 3.5 to 80% by mass, preferably 10 to 60% by mass, and more preferably 15 to 30% by mass.

Furthermore, the protective layer preferably contains an inorganic layered compound for the purpose of improving oxygen barrier properties and image recording layer surface protection. Among inorganic layered compounds, fluorine-based swellable synthetic mica, which is a synthetic inorganic layered compound, is particularly useful. Specifically, inorganic layered compounds described in JP-A No. 2005-119273 are preferable.

The coating amount of the protective layer is preferably 0.05 to 10 g / m ^{2 in} terms of the coating amount after drying, and more preferably 0.1 to 5 g / m ² when an inorganic layered compound is contained. When no layered compound is contained, 0.5 to 5 g / m ² is more preferable.

<Support>
The support used for the photosensitive lithographic printing plate precursor is not particularly limited as long as it is a dimensionally stable plate-like hydrophilic support. In particular, an aluminum plate is preferable. Prior to using the aluminum plate, it is preferable to perform a surface treatment such as roughening treatment or anodizing treatment. The surface roughening treatment of the aluminum plate is performed by various methods. For example, mechanical surface roughening treatment, electrochemical surface roughening treatment (surface roughening treatment for dissolving the surface electrochemically), chemical treatment, etc. Surface roughening treatment (roughening treatment that chemically selectively dissolves the surface). For these treatments, the methods described in JP-A 2007-206217, paragraphs [0241] to [0245] can be preferably used.

The support preferably has a center line average roughness of 0.10 to 1.2 μm. Within this range, good adhesion to the image recording layer, good printing durability and good stain resistance can be obtained.
The color density of the support is preferably 0.15 to 0.65 as a reflection density value. Within this range, good image formability by preventing halation during image exposure and good plate inspection after development can be obtained.
The thickness of the support is preferably from 0.1 to 0.6 mm, more preferably from 0.15 to 0.4 mm.

(Support hydrophilic treatment, undercoat layer)
In the photosensitive lithographic printing plate precursor, in order to improve the hydrophilicity of the non-image area and prevent printing stains, the support surface is hydrophilized or an undercoat layer is provided between the support and the image recording layer. It is also suitable.

Examples of the hydrophilization treatment of the support surface include an alkali metal silicate treatment method in which the support is immersed or electrolyzed in an aqueous solution such as sodium silicate, a treatment method with potassium fluoride zirconate, a treatment method with polyvinylphosphonic acid, etc. The method of immersing in an aqueous polyvinylphosphonic acid solution is preferably used.

As the undercoat layer, an undercoat layer having a compound having an acid group such as phosphonic acid, phosphoric acid or sulfonic acid is preferably used. These compounds preferably further contain a polymerizable group in order to improve adhesion to the image recording layer. As the polymerizable group, an ethylenically unsaturated bond group is preferable. Furthermore, compounds having a hydrophilicity-imparting group such as an ethyleneoxy group can also be mentioned as suitable compounds.
These compounds may be low molecular compounds or high molecular polymers. These compounds may be used as a mixture of two or more if necessary.
A silane coupling agent having an ethylenically unsaturated bond group capable of addition polymerization described in JP-A-10-282679 and a phosphorus compound having an ethylenically unsaturated bond group described in JP-A-2-304441 are suitable. It is mentioned in. A crosslinkable group (preferably an ethylenically unsaturated bond group) described in JP-A-2005-238816, JP-A-2005-12549, JP-A-2006-239867, and JP-A-2006-215263 is formed on the surface of the support. It is also preferable to contain a low molecular or high molecular compound having a functional group that interacts and a hydrophilic group.

The undercoat layer is applied by a known method. The coating amount (solid content) of the undercoat layer is preferably 0.1 ~ 100mg / ^{m 2,} and more preferably 1 ~ 40mg / ^{m 2.}

<Back coat layer>
If necessary, a back coat can be provided on the back surface (surface opposite to the image recording layer) of the support. As the back coat, for example, a layer composed of an organic polymer compound described in JP-A-5-45885, an organic metal compound or an inorganic metal compound described in JP-A-6-35174 is hydrolyzed and Preferred examples include a coating layer made of a metal oxide obtained by polycondensation. Among them, it is inexpensive to use a silicon alkoxy compound such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) ₄ or the like. It is preferable in terms of easy availability.

[Plate making method]
The photosensitive lithographic printing plate precursor according to the present invention is image-exposed and developed to produce a lithographic printing plate. In the waste liquid concentration method of the present invention and the recycling method of the present invention, the development process and the desensitization process are simultaneously performed with a developer in one development processing bath of an automatic developing machine.

[Image exposure process]
The photosensitive lithographic printing plate precursor is exposed imagewise by laser exposure through a transparent original image having a line image, a halftone dot image or the like, or by laser beam scanning by digital data.
The wavelength of the light source is preferably 300 to 450 nm or 750 to 1400 nm. In the case of 300 to 450 nm, a photosensitive lithographic printing plate precursor having a sensitizing dye having an absorption maximum in this region in the image recording layer is used. In the case of 750 to 1400 nm, a sensitizing dye having absorption in this region is used. A photosensitive lithographic printing plate precursor containing an infrared absorber is used. As the light source of 300 to 450 nm, a semiconductor laser is suitable. As the light source having a wavelength of 750 to 1400 nm, a solid laser or semiconductor laser that emits infrared light is suitable. The exposure mechanism may be any of an internal drum system, an external drum system, a flat bed system, and the like.

[Development processing method]
The developer described above can be used as a developer and developer replenisher for the exposed photosensitive lithographic printing plate precursor, and is preferably applied to a developer bath of an automatic processor as described above.
When developing using an automatic processor, the developing solution becomes fatigued according to the amount of processing, so the processing capability may be restored using a replenisher or a fresh developer. This replenishment method is also preferably applied to the recycling method of the present invention.

The development processing can be suitably carried out by an automatic processor equipped with a developer supply means and a rubbing member.
In particular, when the protective layer containing the polyvinyl alcohol is provided on the image recording layer, the photosensitive lithographic printing plate precursor is subjected to laser exposure, and then contains the specific surfactant described above without going through a water washing step, Preferably, with a developer having a pH of 6 to 10, the development treatment for removing the protective layer and the image recording layer in the non-exposed area and the desensitization treatment on the surface of the formed image area are performed in one bath. The amount of processing waste liquid is further reduced as compared with the conventional method in which this is sequentially performed as separate steps.
In addition, prior to the development processing, it is optionally possible to perform a water washing treatment in advance and remove the protective layer.

Further, in the above-described development processing step, the protective layer and the image recording layer of the non-exposed portion are collectively removed, and the formed image portion is subjected to a desensitization process. For this reason, the planographic printing plate obtained after the development processing can be immediately set in a printing machine and printed.
That is, when the specific surfactant is contained in the developer, the development process and the desensitization process are performed in one bath, so that the post-washing process is not particularly necessary, and the drying process can be performed immediately. After the development treatment, it is preferable to dry after removing the excess developer using a squeeze roller.

An example of an automatic developing processor used in the method for preparing a lithographic printing plate according to the present invention will be briefly described with reference to FIG.
The automatic development processor 100 shown in FIG. 3 includes a chamber having an outer shape formed by a machine frame 202, and is continuously formed along the transport direction (arrow A) of the transport path 11 of the photosensitive lithographic printing plate precursor. It has a preheating (preheating) unit 200, a developing unit 300, and a drying unit 400.
The pre-heating unit 200 includes a heating chamber 208 having a carry-in port 212 and a carry-out port 218, and a skewer roller 210, a heater 214, and a circulation fan 216 are disposed therein.

The developing unit 300 is separated from the preheating unit 200 by an outer panel 310, and the outer panel 310 is provided with a slit-shaped insertion port 312.
Inside the developing unit 300, a processing tank 306 having a developing tank 308 filled with a developing solution and an insertion roller pair 304 for guiding the photosensitive lithographic printing plate precursor into the processing tank 306 are provided. The upper part of the developing tank 308 is covered with a shielding lid 324.

Inside the developing tank 308, a guide roller 344 and a guide member 342, a submerged roller pair 316, a brush roller pair 322, a brush roller pair 326, and a carry-out roller pair 318 are arranged in parallel from the upstream side in the transport direction. The photosensitive lithographic printing plate precursor conveyed into the developing tank 308 is immersed in the developer and passes between the rotating brush roller pairs 322 and 326 to remove non-image portions.
A spray pipe 330 is provided below the pair of

brush rollers

322 and 326. The spray pipe 330 is connected to a pump (not shown), and the developer in the developing tank 308 sucked by the pump is ejected from the spray pipe 330 into the developing tank 308.

An overflow port 51 formed at the upper end of the first circulation pipe C1 is provided on the side wall of the developing tank 308, and excess developer flows into the overflow port 51, and the first circulation pipe C1. And is discharged to an external tank 50 provided outside the developing unit 300.
A second circulation pipe C2 is connected to the external tank 50, and a filter portion 54 and a developer supply pump 55 are provided in the second circulation pipe C2. The developer is supplied from the external tank 50 to the developer tank 308 by the developer supply pump 55. In the external tank 50, an upper limit liquid level meter 52 and a lower limit liquid level meter 53 are provided.
The developing tank 308 is connected to the replenishment water tank 71 via the third circulation pipe C3. A water replenishment pump 72 is provided in the third circulation pipe C 3, and water stored in the replenishment water tank 71 is supplied to the developing tank 308 by the water replenishment pump 72.
A liquid temperature sensor 336 is installed upstream of the submerged roller pair 316, and a liquid level meter 338 is installed upstream of the carry-out roller pair 318.

The partition plate 332 disposed between the developing unit 300 and the drying unit 400 is provided with a slit insertion port 334. Further, a shutter (not shown) is provided in the passage between the developing unit 300 and the drying unit 400, and when the planographic printing plate does not pass through the passage, the passage is closed by the shutter.
The drying unit 400 includes a support roller 402,

ducts

410 and 412, a transport roller pair 406,

ducts

410 and 412 and a transport roller pair 408 in this order. A slit hole 414 is provided at the tip of the

ducts

410 and 412. The drying unit 400 is provided with drying means such as hot air supply means and heat generation means (not shown). The drying unit 400 is provided with a discharge port 404, and the planographic printing plate dried by the drying unit is discharged from the discharge port 404.

[Development replenisher replenishment method and reclaimed water replenishment method]
Next, the development replenisher will be described.
In this specification, “development initiator” means an unprocessed developer unless otherwise specified, and “development replenisher” means development treatment of a photosensitive lithographic printing plate precursor or carbon dioxide. It means a developing replenisher that replenishes the developer in the developing bath that has deteriorated due to the absorption of water.
The composition of the development replenisher is basically the same as the composition of the above-mentioned development starter. However, if necessary, it has a higher activity than the development starter in order to recover the activity of the deteriorated developer. May be.

The development starting solution initially charged in the developing bath of the automatic developing machine 10 is deteriorated by the eluate generated by the processing of the photosensitive lithographic printing plate precursor. Therefore, in order to perform development processing continuously for a long period of time in the automatic developing machine 10, normally, in order to maintain the development quality of the photosensitive lithographic printing plate precursor, at least either a development replenisher or water that compensates for deterioration is used. One of them needs to be replenished intermittently or continuously.
As for a specific replenishment method, (1) a developer having the same concentration as that of the first charged development start solution is replenished, and (2) a developer having the same concentration as that of the first charged development start solution and water which is volatilized. (3) Replenish developer solution with high concentration + water (4) Four patterns for replenishing only the water that has been volatilized are conceivable.
In the case of (1), specifically, the developer concentrated solution is diluted with regenerated water in advance to obtain a developer having the same concentration as that of the initially developed developer, and then replenished. In the cases (2) and (3), the developer and water are replenished independently, and the reclaimed water is used as an evaporation correction. In the case of (4), only reclaimed water is replenished.

[Other plate making processes]
In addition, as a plate making process for producing a lithographic printing plate from the photosensitive lithographic printing plate precursor according to the present invention, the entire surface may be heated before exposure, during exposure, and between exposure and development, if necessary. By such heating, an image forming reaction in the image recording layer is promoted, and advantages such as improvement in sensitivity and printing durability and stabilization of sensitivity may occur. Further, for the purpose of improving the image strength and printing durability, it is also effective to subject the developed image to full post heating or full exposure. Usually, the heating before development is preferably performed under a mild condition of 150 ° C. or less. If the temperature is too high, problems such as covering up to the non-image area occur. Very strong conditions are used for heating after development. Usually, it is in the range of 200 to 500 ° C. If the temperature is low, sufficient image strengthening action cannot be obtained. If the temperature is too high, problems such as deterioration of the support and thermal decomposition of the image area occur.

Hereinafter, the present invention will be described in detail with specific examples, but the present invention is not limited to the following description.
[Example 1]
1. Preparation of photosensitive lithographic printing plate precursor 1 [Preparation of aluminum support 1]
In order to remove rolling oil on the surface of an aluminum plate (material: JIS A1050) having a thickness of 0.3 mm, after degreasing at 50 ° C. for 30 seconds using a 10 mass% sodium aluminate aqueous solution, the hair diameter is 0.3 mm. The aluminum surface was grained with three bundle-planted nylon brushes and a pumice-water suspension (specific gravity 1.1 g / cm ³ ) having a median diameter of 25 μm and thoroughly washed with water. This plate was etched by being immersed in a 25 mass% sodium hydroxide aqueous solution at 45 ° C for 9 seconds, washed with water, further immersed in a 20 mass% nitric acid aqueous solution at 60 ° C for 20 seconds, and washed with water. The etching amount of the grained surface at this time was about 3 g / m ² .

Next, an electrochemical roughening treatment was performed continuously using an alternating voltage of 60 Hz. The electrolytic solution at this time was a 1% by mass aqueous solution of nitric acid (containing 0.5% by mass of aluminum ions) and a liquid temperature of 50 ° C. The AC power supply waveform is electrochemical roughening treatment using a trapezoidal rectangular wave AC with a time TP of 0.8 msec until the current value reaches a peak from zero, a duty ratio of 1: 1, and a trapezoidal rectangular wave AC. Went. Ferrite was used for the auxiliary anode. The current density was 30 A / dm ² at the peak current value, and 5% of the current flowing from the power source was shunted to the auxiliary anode. The amount of electricity in the nitric acid electrolysis was 175 C / dm ² when the aluminum plate was the anode. Then, water washing by spraying was performed.

Next, a 0.5% by mass hydrochloric acid aqueous solution (containing 0.5% by mass of aluminum ions) and an electrolytic solution having a liquid temperature of 50 ° C. and nitric acid electrolysis under the condition of an electric quantity of 50 C / dm ² when the aluminum plate is an anode. In the same manner as above, an electrochemical surface roughening treatment was performed, followed by washing with water by spraying. A DC anodized film of 2.5 g / m ² was provided on the plate aluminum using a 15% by mass sulfuric acid aqueous solution (containing 0.5% by mass of aluminum ions) as an electrolyte under a current density of 15 A / dm ² . Thereafter, it was washed with water and dried to produce an aluminum support 1.
The center line average roughness (Ra) of the support thus obtained was measured using a needle having a diameter of 2 μm and found to be 0.51 μm.

[Preparation of Aluminum Support 2]
The aluminum support 1 was treated with a 1% by mass aqueous solution of sodium silicate at 20 ° C. for 10 seconds to produce an aluminum support 2. When the surface roughness was measured, it was 0.54 μm (Ra display according to JIS B0601).

(Formation of undercoat layer)
The following undercoat layer coating solution (1) was applied to the aluminum support 2 using a bar coater and dried at 80 ° C. for 20 seconds to prepare a support 3. The coating amount of the undercoat layer after drying was 15 mg / m ² .

<Undercoat layer coating solution (1)>
The following polymer (SP3) 2.7 g
900.0g of pure water
Methanol 100.0g

[Formation of Image Recording Layer 1]
An image recording layer coating solution 1 having the following composition is bar-coated on the undercoat layer of the support 3 and then oven-dried at 90 ° C. for 60 seconds to form an image recording layer 1 having a dry coating amount of 1.3 g / m ^2. did.

<Image recording layer coating solution 1>
-The following binder polymer (1) (mass average molecular weight: 80,000) 0.34 g
・ The following polymerizable compound (1) 0.68 g
(PLEX6661-O, manufactured by Degussa Japan)
・ The following sensitizing dye (1) 0.06 g
・ The following polymerization initiator (1) 0.18 g
・ The following chain transfer agent (1) 0.02 g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (mass average molecular weight: 60,000, copolymer molar ratio: 83/17)):
(10 parts by mass, cyclohexanone: 15 parts by mass)
-Thermal polymerization inhibitor (N-nitrosophenylhydroxylamine aluminum salt) 0.01g
-The following fluorosurfactant (1) (mass average molecular weight: 10,000)
0.001g
・ Polyoxyethylene-polyoxypropylene condensate 0.02g
(Pluronic L44, manufactured by ADEKA Corporation)
・ Dispersion of yellow pigment 0.04g
(Yellow pigment Novoperm Yellow H2G (manufactured by Clariant): 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (mass average molecular weight: 60,000, copolymer molar ratio 83/17)): 10 parts by mass, and solvent As a cyclohexanone containing 15 parts by mass)
・ 3.5g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g

[Formation of Protective Layer 1]
A protective layer coating solution 1 having the following composition was coated on the image recording layer 1 using a bar so that the dry coating amount was 1.5 g / m ^2, and then dried at 125 ° C. for 70 seconds for protection. A layer was formed to obtain a photosensitive lithographic printing plate precursor 1.

<Protective layer coating solution 1>
・ Mica dispersion (1) 0.6g
・ Sulphonic acid-modified polyvinyl alcohol 0.73g
(Goceran CKS-50, manufactured by Nippon Synthetic Chemical Co., Ltd., degree of saponification:
99 mol%, average degree of polymerization: 300, degree of modification: about 0.4 mol%)
・ Poly (vinyl pyrrolidone / vinyl acetate (1/1)) 0.001 g
(Mass average molecular weight: 70,000)
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.002g
・ Water 13g

(Preparation of mica dispersion (1))
To 368 g of water, 32 g of synthetic mica (Somasif ME-100, manufactured by Corp Chemical Co., aspect ratio: 1000 or more) was added and dispersed using a homogenizer until the average particle size (laser scattering method) became 0.5 μm. A dispersion (1) was obtained.

[Exposure of photosensitive lithographic printing plate precursor]
Photosensitive lithographic printing plate precursor 1 was prepared from FUJIFILM Electronic Imaging Ltd. Image exposure was performed with a Violet semiconductor laser plate setter Vx9600 (InGaN-based semiconductor laser (with an emission wavelength of 405 nm ± 10 nm / output 30 mW) mounted) manufactured by (FFEI). Image exposure was carried out at a resolution of 2438 dpi using an FM screen (TAFFETA 20) manufactured by FUJIFILM Corporation with a plate surface exposure of 0.05 mJ / cm ² so that the dot area ratio was 50%.
Next, preheating was performed at 100 ° C. for 30 seconds.

[Development process]
The photosensitive lithographic printing plate precursor after the exposure was developed using an automatic developing processor having a structure as shown in FIG. The automatic processor has one brush roll having an outer diameter of 50 mm in which fibers made of polybutylene terephthalate (hair diameter 200 μm, hair length 17 mm) are implanted, and the brush roll is provided in the same direction as the transport direction. The rotation speed was 200 revolutions per minute (the peripheral speed of the brush tip was 0.52 m / sec). The temperature of the developer was 30 ° C. The photosensitive lithographic printing plate precursor was transported at a transport speed of 100 cm / min. After the development processing, drying was performed in a drying section. The drying temperature was 80 ° C.

<Developer 1>
・ Sodium carbonate 1.30g
・ Sodium bicarbonate 0.7g
Specific nonionic surfactant or specific anionic surfactant [Compound described in Table 1] Amount (g) described in Table 1
Organic solvent [compounds listed in Table 1] Amounts listed in Table 1 (g)
Specific betaine surfactant [compound described in Table 1] amount described in Table 1 (g)
・ Surfinol DF-110D 0.05g
・ Primary ammonium phosphate 0.2g
・ 0.001 g of 2-bromo-2-nitropropane-1,3-diol
・ 2-Methyl-4-isothiazolin-3-one 0.001g
・ Trisodium citrate 1.50 g
・ Distilled water Added to a total of 100 g (pH: 9.8)
The structure of the surfactant used in the developer is shown below. Surfactants (R-1) and (R-2) are comparative surfactants having no phenyl group or naphthyl group.

“-” In Table 1 means that no betaine-type surfactant is contained.

[Waste liquid concentration process and reclaimed water generation process]
After the developer 100L (20L in the developing tank and 80L in the external tank) is charged into the automatic developing machine, the plate making process is continuously performed for the photosensitive lithographic printing plate precursor 1500m ² without changing or replenishing the developer. Thereafter, the developing solution was drained. The obtained effluent was passed through a waste liquid concentrator XR-2000 manufactured by FFGS, and concentrated so as to have a concentration rate shown in Table 2 below (waste liquid concentration step).
(Evaluation of planographic printing plate after plate making)
The photosensitive lithographic printing plate precursor 1500 m ² was continuously subjected to plate making treatment, and then the development state of the lithographic printing plate obtained after plate making treatment was visually examined and evaluated according to the following criteria.
No problem: Good development state Development failure: Image recording layer remains in non-image area due to development failure Over-development: Image area is missing due to over-development and image defects occur : In the developing tank, debris resulting from precipitation of developed components and the like is generated and adhered to the plate (evaluation of the concentrated liquid in the waste liquid concentration process)
When the waste liquid was concentrated in the waste liquid concentration step, the foamability and precipitation of the waste liquid in the concentration apparatus were examined. In the case where the solid content was precipitated in the apparatus or the foamed portion was generated, the water vapor separated here was unsuitable as reclaimed water and was not used.
(Evaluation of reclaimed water generation process and reclaimed water)
Water vapor evaporated and separated in the waste liquid concentrator XR-2000 manufactured by FFGS was condensed to obtain reclaimed water.
The presence or absence of a solvent in the obtained reclaimed water was confirmed. Those that were confirmed to contain the solvent were not used as recycled water because they affected the formulation of the developer.

“-” In Table 2 means that evaluation is not performed.

[Reclaimed water supply process]
Of the reclaimed water obtained through the waste liquid concentration step and the subsequent reclaimed water generation step, the reclaimed water that did not cause a problem by the above evaluation is used as reclaimed water. The required amount was circulated in the developing bath of the developing machine.
Thereafter, using the developers of Invention Product 1 to Invention Product 13 and performing continuous plate-making treatment while supplying reclaimed water obtained from these developers as replenishing water, In the 1500 m ² continuous plate-making process of the photosensitive lithographic printing plate precursor, good plate-making was performed, and no problem was caused.

[Example 2]
2. Preparation of photosensitive lithographic printing plate precursor 2 <Preparation of support 4>
An aluminum plate (material 1050, tempered H16) having a thickness of 0.24 mm was immersed in a 5% by mass aqueous sodium hydroxide solution maintained at 65 ° C., degreased for 1 minute, and then washed with water. The aluminum plate was neutralized by immersing it in a 10% by mass hydrochloric acid aqueous solution maintained at 25 ° C. for 1 minute, and then washed with water. Next, the aluminum plate was subjected to electrolytic surface roughening with an alternating current for 60 seconds under conditions of 25 ° C. and a current density of 100 A / dm ^{2 in} a 0.3 mass% hydrochloric acid aqueous solution, and then the temperature was increased to 60 ° C. The desmutting treatment was carried out for 10 seconds in the maintained 5 mass% aqueous sodium hydroxide solution. This aluminum plate was anodized in a 15% by weight sulfuric acid aqueous solution at 25 ° C., a current density of 10 A / dm ² and a voltage of 15 V for 1 minute, and further immersed in a 1% by weight polyvinyl phosphonic acid aqueous solution at 60 ° C. for 10 seconds. After that, the substrate 4 was washed with hard water having a calcium ion concentration of 75 ppm at 20 ° C. and then with pure water for 4 seconds, subjected to a hydrophilic treatment, and dried to prepare the support 4. The adhesion amount of calcium was 2.0 mg / m ² . It was 0.44 micrometer (Ra display by JISB0601) when the surface roughness of the support body 4 was measured.

<Formation of Image Recording Layer 2>
An image recording layer coating liquid (2) having the following composition was bar-coated on the support 4 and then oven-dried at 90 ° C. for 60 seconds to form an image recording layer 2 having a dry coating amount of 1.3 g / m ² . .

<Image recording layer coating solution (2)>
・ The following binder polymer (1) (mass average molecular weight: 50,000) 0.04 g
-The following binder polymer (2) (mass average molecular weight: 80,000) 0.30 g
・ The following polymerizable compound (1) 0.17 g
(PLEX6661-O, manufactured by Degussa Japan)
-0.51 g of the following polymerizable compound (2)
・ The following sensitizing dye (1) 0.03 g
・ The following sensitizing dye (2) 0.015 g
・ The following sensitizing dye (3) 0.015 g
・ The following polymerization initiator (1) 0.13 g
・ Chain transfer agent: Mercaptobenzothiazole 0.01g
・ 0.40 g of ε-phthalocyanine pigment dispersion
(Pigment: 15 parts by mass, dispersant (allyl methacrylate / methacrylic acid copolymer (mass average molecular weight: 60,000, copolymer molar ratio: 83/17)): 10 parts by mass, cyclohexanone: 15 parts by mass)
・ Thermal polymerization inhibitor 0.01g
N-nitrosophenylhydroxylamine aluminum salt-Fluorosurfactant (1) below (mass average molecular weight: 10,000) 0.001 g
・ 3.5g of 1-methoxy-2-propanol
・ Methyl ethyl ketone 8.0g
・ N, N dimethylaminopropyl methacrylamide 0.015g

[Formation of Protective Layer 2]
A protective layer coating solution 2 having the following composition was coated on the image recording layer 2 using a bar so that the dry coating amount was 1.2 g / m ^2, and then dried at 125 ° C. for 70 seconds. A protective layer 2 was formed, and a photosensitive lithographic printing plate precursor 2 was obtained.

<Protective layer coating solution 2>
・ Polyvinyl alcohol (degree of saponification: 98 mol%, degree of polymerization: 500) 40 g
・ Polyvinylpyrrolidone (molecular weight: 50,000) 5g
・ Poly [vinyl pyrrolidone / vinyl acetate (1/1)] (molecular weight: 70,000) 0.5 g
・ Surfactant (Emalex 710, manufactured by Nippon Emulsion Co., Ltd.) 0.5g
・ 950g of water

<Developer 2>
Specific nonionic surfactant or specific anionic surfactant [Compound described in Table 3] Amount (g) described in Table 3
Organic solvent [compound described in Table 3] Amount described in Table 3 (g)
・ Triethanolamine 0.5g
・ Sodium gluconate 1.0g
・ Trisodium citrate 0.5g
・ Ethylenediaminetetraacetate tetrasodium 0.05g
・ Polystyrenesulfonic acid 1.0g
(Versa TL77 (30% by mass solution), manufactured by Alco Chemical)
(Phosphoric acid is added and adjusted to the pH shown in Table 4)
-Water Added so that the total is 100 g. The structure of each surfactant and solvent (S) used in the developer is shown below. Surfactant (R-3) is a comparative surfactant having no phenyl group or naphthyl group.

[Development process]
The photosensitive lithographic printing plate precursor after the exposure was developed using an automatic developing processor having a structure as shown in FIG. 3 using each developer shown in Table 3 below. The automatic processor has one brush roll having an outer diameter of 50 mm in which fibers made of polybutylene terephthalate (hair diameter 200 μm, hair length 17 mm) are implanted, and the brush roll is provided in the same direction as the transport direction. The rotation speed was 200 revolutions per minute (the peripheral speed of the brush tip was 0.52 m / sec). The temperature of the developer was 30 ° C. The photosensitive lithographic printing plate precursor was transported at a transport speed of 100 cm / min. After the development processing, drying was performed in a drying section. The drying temperature was 80 ° C.

[Waste liquid concentration process and reclaimed water generation process]
Instead of the product 1 of the present invention as the developer, the developers of the products 14 to 22 and comparative products 9 to 14 shown in Table 3 above are used, and the photosensitive lithographic printing plate precursor 1 is used instead of the photosensitive lithographic printing plate precursor 1. Table 4 below shows the results of a similar evaluation performed in the same manner as in Example 1 except that the original plate 2 was subjected to the continuous plate making process, the waste liquid concentration step, and the recycled water generation step of the photosensitive lithographic printing plate precursor.

“-” In Table 4 means that evaluation is not performed.

[Reclaimed water supply process]
Also in the above-described embodiment, when the inventive products 14 to 22 were used as the developer, as in the case of the inventive product 1, regenerated water was supplied for further continuous plate-making treatment. It was confirmed that good plate making was performed.

As is apparent from Tables 2 and 4, according to the method for concentrating a plate making waste liquid of the present invention, the development process and the desensitization process can be simultaneously performed in one developing bath, and there is a recycled water suitable for recycling. It can be seen that it is generated. On the other hand, when a developer outside the scope of the present invention is used, there is a problem that a solvent is mixed in the reclaimed water, or solid matter is precipitated in the concentration step, resulting in good reduction of waste liquid and generation of reclaimed water. I could not do it.

The disclosure of Japanese application 2012-034569 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually described to be incorporated by reference, Incorporated herein by reference.

Claims

The photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on the support is exposed to the photosensitive lithographic printing plate precursor after exposure in one development processing bath of an automatic developing machine. An organic solvent containing 1% by mass to 10% by mass of a surfactant having a phenyl group or a naphthyl group and at least one of an ethylene oxide group or a propylene oxide group, and having a boiling point in the range of 100 ° C. to 300 ° C. A plate making process step in which the development process and the desensitization process are simultaneously performed with a developer having an amount of 2% by mass or less and a boiling point of substantially lower than 100 ° C. or higher than 300 ° C.
The platemaking process waste liquid generated in the platemaking process is evaporated and concentrated by a waste liquid concentrator so that the ratio of the volume of the platemaking process liquid after concentration / the volume of the platemaking process waste liquid before concentration is 1/2 to 1/10. Waste liquid concentration step, and
A reclaimed water generating step for condensing the water vapor separated in the waste liquid concentration step to generate reclaimed water,
A method for concentrating a lithographic processing waste solution of a photosensitive lithographic printing plate precursor containing
2. The method of concentrating a plate making waste liquid of a photosensitive lithographic printing plate precursor according to claim 1, wherein the pH of the developer is 6 to 10.
The photosensitive lithographic printing plate precursor having a radically polymerizable image recording layer on the support is exposed to the photosensitive lithographic printing plate precursor after exposure in one development processing bath of an automatic developing machine. An organic solvent having 1 to 10% by mass of a surfactant having a phenyl group or naphthyl group and at least one of an ethylene oxide group and a propylene oxide group and having a boiling point in the range of 100 ° C. to 300 ° C. A plate making process step in which the development process and the desensitization process are simultaneously performed with a developer having a content of 2% by mass or less and a boiling point of substantially lower than 100 ° C. or higher than 300 ° C.
The platemaking process waste liquid generated in the platemaking process is evaporated and concentrated by a waste liquid concentrator so that the ratio of the volume of the platemaking process liquid after concentration / the volume of the platemaking process waste liquid before concentration is 1/2 to 1/10. Waste liquid concentration process,
A regenerated water generating step for condensing the water vapor separated in the waste liquid concentration step to generate regenerated water, and
A reclaimed water supply step of supplying reclaimed water obtained in the reclaimed water generating step to the automatic processor;
Recycling method of waste liquid for plate making treatment of photosensitive lithographic printing plate precursor containing
The method for recycling a platemaking treatment waste liquid according to claim 3, wherein the surfactant has 5 to 30 of at least one of the ethylene oxide group and the propylene oxide group.
The developer further contains at least one compound represented by the following general formula <1>, general formula <2>, and general formula <3>, and includes the following general formula <1> and general formula <2 > And the total content in the developer of the compound represented by the general formula <3> is less than 10% by mass, the method of recycling a platemaking waste liquid according to claim 3 or 4.

In the general formula <1>, R 1 represents a hydrogen atom, an alkyl group, or a substituent having the following structure. A represents a hydrogen atom, an alkyl group, a monovalent substituent including an ethylene oxide group, a monovalent substituent including a carboxylic acid group, or a monovalent substituent including a carboxylate, and B represents an ethylene oxide group. The monovalent substituent containing, the monovalent substituent containing a carboxylic acid group, or the monovalent substituent containing a carboxylate is represented.

In the above formula, R 8 represents a hydrogen atom or an alkyl group.
In the general formula <2>, R 2 and R 3 each independently represent a hydrogen atom or an alkyl group which may have a substituent, and at least one of R 2 and R 3 has a substituent. Represents an optionally substituted alkyl group.
D represents an alkyl group or a monovalent substituent containing an ethylene oxide group, and E represents a monovalent substituent containing a carboxylate anion or a monovalent substituent containing an oxide anion (O − ).
In the general formula <3>, R 4 , R 5 , R 6 and R 7 each independently represent a hydrogen atom or an alkyl group, and Z − represents a counter anion.
The method for recycling a platemaking treatment waste liquid according to any one of claims 3 to 5, wherein the pH of the developer is 6 to 10.
The lithographic printing plate obtained by performing the development process and the desensitization process on the photosensitive lithographic printing plate precursor after the exposure further includes drying the lithographic printing plate. The recycling method of the plate-making process waste liquid of Claim 1.
Before performing the development process and the desensitization process, the exposed photosensitive lithographic printing plate precursor is subjected to a heat treatment, and the development process and the desensitized fat are performed on the exposed photosensitive lithographic printing plate precursor. The method of recycling a platemaking waste liquid according to any one of claims 3 to 6, further comprising: drying the lithographic printing plate obtained by performing the crystallization treatment.
The method of recycling a platemaking process waste liquid according to any one of claims 3 to 8, wherein the waste liquid concentrator has a heating means.
The method for recycling a platemaking process waste liquid according to claim 9, wherein the heating by the heating means of the waste liquid concentrator is performed in a reduced pressure state.
The heating means of the waste liquid concentrator is a heat pump including a heat radiating part and a heat absorbing part, the plate making waste liquid is heated by the heat radiating part of the heat pump, and the water vapor is cooled by the heat absorbing part of the heat pump. The recycling method of the platemaking process waste liquid of Claim 9 or Claim 10.
The concentrate according to any one of claims 3 to 11, wherein the waste liquid concentration step includes a concentrate recovery step of pressurizing the concentrate of the plate-making process waste liquid concentrated by evaporation and pumping the concentrate to a recovery tank. Recycling method of platemaking waste liquid as described.